Heterometallic thiocubanes (C-2044)

ABSTRACT

This invention relates to heterometallic thiocubane compositions containing the M 2   1  M 2   2  S 4  cluster core and methods of making them wherein M 1  is Re, V, Mo or W and M 2  is Co, Cr, Cu, Ni or Fe but preferably Co. More particularly, the invention relates to compositions of the formula M 2   2  M 2   2  S 4  L 2   1  L 2   2  L 2   3  wherein M 1  and M 2  are as above, L 1  is a bidentate sulfur or nitrogen bearing ligand (most preferably a dialkyldithiocarbamate), L 2  is optional but may be an O, N, P or S-containing monodentate donor ligand, and L 3  may be CO, a monodentate anion ligand such as a halide (preferably C1), mercaptide or alkoxide, or another O, N, P, or S containing monodentate donor ligand. The compositions are suitable for making active hydrotreating catalysts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 711,601, filed Mar. 14, 1985 now abandoned.

FIELD OF THE INVENTION

This invention relates to heterometallic thiocubane compositions containing the M₂ ¹ M₂ ² S₄ cluster core and methods of making them wherein M¹ is Re, V, Mo or W but preferably Mo or W; and M² is Co, Cr, Cu, Ni, or Fe but preferably Co. More particularly, the invention relates to compositions of the formula M₂ ¹ M₂ ² S₄ L₂ ¹ L₂ ² L₂ ³ wherein M¹ and M² are as above, L¹ is a bidentate sulfur and/or nitrogen bearing ligand (desirably a dithiolate and preferably a dialkyldithiocarbamate), L² is optional and may be an O, N, P, or S-containing monodentate donor ligand, and L³ may be CO, a monodentate anion ligand such as a halide (preferably Cl), mercaptide or alkoxide, or another O, N, P, or S containing monodentate donor ligand. The compositions are suitable for making active hydrotreating catalysts.

BACKGROUND OF THE INVENTION

Thiocubane clusters containing a homometallic core M₄ S₄ are known in the art. The thiocubane core is so-named because of its molecular architecture, i.e., two tetrahedra of metal and sulfur atoms interlock so that the metal atoms and bridging sulfurs occupy the alternate corners of a distorted or approximate cube. Homometallic thiocubane structures containing, e.g., Co, Fe, Mo, have been synthesized and discussed at length in the chemical literature. See, e.g., Mak et al, Angew. Chem. Int. Ed. Engl. 23 (1984), pp. 391-2; shibahara et al, J. Am. Chem. Soc. (1984), 106, pp. 789-791; Chu et al, J. Am. Chem. Soc. (1982), v. 104, pp. 3409-3422 (and references cited therein) and Simon et al, J. Am. Chem. Soc. (1973), v. 95, pp. 2164-2174.

Compositions containing heterometallic thiocubane clusters have also been studied. The particular interest in the Fe₂ MoS₄ cluster, because of its possible function as the biologically active part of nitrogenase, has led to the attempted synthesis of other similar compositions. See, e.g., Curtis et al, Inorg. Chem., v. 22, pp. 2661-2; Brunner et al, Agnew. Chem. Int. Ed. Engl 22 (1983), pg. 549; Brunner et al, J. Organometallic Chem., 240 (1982) C41-C44; Holm, Chem. Soc. Rev. (1981), v. 10, p. 455; and Armstrong et al., Inorg. Chem. (1982) v. 21, 1699-1701.

In addition to the interest shown in the bimetallic thiocubane cluster as a biologically active enzyme constituent, others have suggested that sulfided clusters containing molybdenum and a Group VIII metal, e.g., Fe, Co or Ni, may be useful as models in clarifying the somewhat poorly understood activity of hydrodesulfurization catalysts based on "sulfided" iron, cobalt, or nickel molybdates and tungstates on oxide supports. See, Curtis et al, supra, and the references cited therein; Gates et al, "Chemistry of Catalytic Processes", McGraw-Hill, New York (1979), pp. 390-445.

In the earlier syntheses of the thiocubane core, the approach was typically "spontaneous assembly". See, Holm, supra. Later work in homometallic transition metal sulfide chemistry led to smaller clusters which could be considered fragments of the thiocubane unit. These fragments, e.g., Cp₂ M₂ S₄ and related compounds (where Cp represents the cylcopentadienyl ligand), are potential building blocks for heteronuclear thiocubane clusters and can be used to form clusters with M₂ M₂ '(μ³ -S)₄ cores. See, the two Brunner et al articles, supra.

None of the prior art shows the synthesis of M₂ ¹ M₂ ² (μ³ -S)₄ L₂ ¹ L₂ ² L₂ ³ where M¹ is Re, V, Mo or W, M² is Co, Cr, Cu, Ni or Fe, L¹ is a bidentate sulfur and/or nitrogen bearing ligand, and L² is optional but may be an S, N, P, or O monodentate donor ligand, e.g., a solvent or other Lewis base molecule, and L³ may be CO, a monodentate anion ligand such as a halide (preferably Cl), mercaptide or alkoxide, or another O, N, P, or S containing monodentate donor ligand.

SUMMARY OF THE INVENTION

This invention deals with compositions containing heterometallic thiocubane nuclei. In particular the compositions have the generalized formula M₂ ¹ M₂ ² (μ³ -S)₄ L₂ ¹ L₂ ² L₂ ³ where M¹ is Re, V, Mo or W (but preferably Mo or W); M² is Co, Cr, Cu, Ni or Fe (but preferably Co); L¹ is a bidentate sulfur and/or nitrogen bearing ligand such as dithiolates and particularly xanthate, o-aminobenzenethiolate, dithiophosphinate, dithiophosphate (but preferably a dithiocarbamate (S₂ CNR₂) where R is independently H, or a hydrocarbyl such as methyl, ethyl, propyl, butyl, phenyl or mixtures of such groups, but preferably ethyl); L² is optional but may be an S, N, P, or O monodentate donor ligand, e.g., a solvent or other Lewis base molecule such as a pyridine, ether or phosphine ligand (but is preferably acetonitrile); and L³ may be CO, a monodentate anion ligand such as a halide (preferably Cl), mercaptide or alkoxide, or another O, N, P, or S containing monodentate donor ligand.

The heterometallic thiocubane composition is preferably synthesized using novel dimeric neutral complexes of, e.g., tungsten, sulfide and dialkyldithiocarbamates.

The heterometallic thiocubane compositions have various uses but are especially useful in the preparation of catalysts for hydrotreating hydrocarbons containing sulfur-bearing compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a molecular depiction of one composition, i.e., Mo₂ Co₂ (μ³ -S)₄ ((C₂ H₅)₂ NCS₂)₂ (CO)₂ (CH₃ CN)₂, within the scope of the invention.

FIG. 2 is a molecular depiction of one composition, i.e., Mo₂ Cu₂ (μ³ -S)₄ ((C₄ C₉)₂ NCS₂)₂ (Cl)₂, within the scope of the invention.

DESCRIPTION OF THE INVENTION

The invention, as noted above, is generically a composition of matter containing certain heterometallic thiocubane clusters. The broad formula for the composition is:

    M.sub.2.sup.1 M.sub.2.sup.2 (μ.sup.3 -S).sub.4 L.sub.2.sup.1 L.sub.2.sup.2 L.sub.2.sup.3

where:

M¹ is Re, V, Mo or W; preferably Mo or W;

M² is Co, Cr, Cu, Ni or Fe; preferably Co;

L¹ is a bidentate sulfur and/or nitrogen-bearing ligand such as amino benzene thiolate or dithiolates, particularly xanthate, dithiophosphinate, dithiophosphate, dithiocarbamate, etc.; preferably dithiocarbamate (S₂ CNR₂) where R is independently an H or a hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl, most preferably ethyl; other suitable ligands include those having the formula: C₆ H₄ SNH₂, SCH₂ CH₂ S, and CH₃ NHCH₂ (CH₃)₂ S.

L² is optional but may be a monodentate S, N, P, or O donor ligand, e.g., a solvent or other Lewis base molecule such as a pyridine, ether or phosphine but preferably acetonitrile. The thiocubane core is, however, stable without the presence of L².

L³ may be CO, a monodentate anion ligand such as a halide (preferably Cl), mercaptide or alkoxide, or another O, N, P, or S containing monodentate donor ligand.

The preferred method of synthesizing the inventive heterometallic thiocubanes involves the addition of a generally stoichiometric amount of a low valent complex based upon one of the "M² " metals Co, Cr, Cu, Ni or Fe such as Co₂ (CO)₈, Ni(CO)₄, or CuCl to a solution or slurry of M₂ ¹ S₄ L₂ ¹. The metal M¹, as above, may be Re, V, Mo or W although preferably is Mo or W. To achieve the goal of including substantial sulfur in a hydrodesulfurization catalyst using the inventive compound as a precursor, the bidentate ligand should be a mono- or a dithiolate. Although a large number of such ligands may be used, e.g., amino benzene thiolates, xanthates, dithiophosphinates, dithiophosphates, the preferred ligand is a dithiocarbamate of the formula S₂ CNR₂ wherein R is independently H or a hydrocarbyl or alkyl of C₁ to C₁₂. The diethyl form is especially preferred.

These two materials may be placed together in a suitable solvent which may, by default, act as the monodentate ligand L² (or L³) above. Acetonitrile is especially useful.

These "inorganic synthons" obviously act as building blocks to the final inventive heterometallic thiocubane composition. The reaction usually proceeds at room temperature with no heat input required.

Although the syntheses of a majority of the materials used in producing the thiocubanes are known, the production of one such fragment is not, i.e., W₂ S₄ (S₂ CNR₂)₂ where R is an H or a C₁ to C₁₂ hydrocarbyl group.

These fragments may be made by gently heating (NEt₄)₂ W₂ S₁₂ in an acetonitrile solution, or other aprotic solvent, in the presence of R₂ NCS₂ ⁻, NH₄ ⁺, and P(C₆ H₅)₃. When making the tungsten-based compound, the product is found in and may be isolated from an orange slurry.

This process may be used to produce compounds of the formula:

    W.sub.2 S.sub.4 (S.sub.2 CNR.sup.1 R.sup.2).sub.2

where R^(n) =H, an alkyl of 1 to 12 carbon atoms, and aryl groups of 6 to 12 carbamates. R¹ need not be the same as R²

and also

    W.sub.2 S.sub.4 (S.sub.2 COR).sub.2

where R are alkyl or aryl groups of the type discussed above.

Having thus described the invention in detail, following are a number of examples which further delineate the invention. These examples are not intended to be limiting in any manner to the invention claimed below.

EXAMPLE 1 Production of (NEt₄)₂ W₂ S₁₂

Excess sulfur (1.18 g, 4.60 mmol) was added to a stirred solution of (NH₄)₂ WS₄ (3.20 g, 9.20 mmol) in 50 mL DMF and heated two hours at 110° while purging slowly with Ar. The resulting orange-red solution was allowed to cool, excess NEt₄ Br (2.55 g, 12.1 mmol) was added, and the mixture heated at 110° for an additional 60 min. Volatiles were removed at 60° under vacuum, leaving an oily orange-red solid. Repeated recrystallization of the product from acetonitrile with intermittent washings with toluene, methanol, and diethylether yielded 3.85 g (83%) of red crystalline (NEt₄)₂ W₂ S₁₂.

Anal. Calcd for C₁₆ H₄₀ N₂ S₁₂ W₂ : C, 18.97, H, 3.98, N, 2.77, S, 37.98, W, 36.30. Found: C, 19.00, H, 3.86, N, 2.68, S, 37.44, W. 36.25. IR: 3000 (w), 2980 (w), 1474 (s), 1445 (m), 1432 (m), 1417 (w), 1390 (m), 1385 (m), 1312 (m), 1184 (w), 1168 (s), 1065 (w), 1049 (w), 996 (s), 777 (s), 506 (vs), 495 (sh), 460 (w), 423 (m), 414 (m), 405 (sh), 380 (m), 371 (w), 294 (m) cm⁻¹. FAB-MS (in tetramethylenesulfone) m/e for parent negative ion [(NEt₄)W₂ S₁₂ ]⁻ (rel. abundance calc, exp): 878 (19,25); 879 (23,28); 880 (62,62); 881 (45,51); 882 (100,100), 883 (55,61); 884 (96,98); 885 (32,42); 886 (60,62); 887 (14,19); 888 (21,25). ¹⁸³ W NMR (1.11 g (NEt₄)₂ W₂ S₁₂ in 2.2 mL DMF and 0.7 mL DMF-d₇): 2131.

EXAMPLE 2 Production of W₂ S₄ (S₂ CNEt₂)₂

An acetonitrile solution of (50 ml) containing PPh₃ (0.8 g, 3 mmol), NH₄ PF₆ (0.48 g, 2.9 mmol), Na(S₂ CNEt₂).3H₂ O (0.35 g, 1.6 mmol), and (NEt₄)₂ W₂ S₁₂ (0.508 g, 0.502 mmol) made according to Example 1 was heated at 75° for 45 min., resulting in the formation of an orange slurry. Volatiles were removed in vacuo, leaving a mixture of orange and white solids. The mixture was cooled to 0° and washed with 2×15 ml CH₃ OH, 2×20 ml acetone, and 3×20 ml ether. The resulting orange powder was dried under vacuum. Yield was 300 mg (75%). Air-stable W₂ S₄ (S₂ CNEt₂)₂ is very slightly soluble in DMF and hot acetonitrile.

Anal. Calcd. for C₁₀ H₂₀ N₂ S₈ W₂ : C, 15.16; H, 2.54; N, 3.53; S, 32.36. Found: C, 14.94; H, 2.30; N, 3.57; S, 32.34. IR: 2980 (w), 2935 (w), 1530 (s), 1456 (m), 1440 (m), 1382 (w), 1358 (m), 1297 (w), 1281 (s), 1201 (m), 1152 (m), 1098 (w), 1077 (m), 1006 (w), 996 (w), 908 (w), 847 (w), 779 (w), 527 (s), 519 (s), 445 (m), 371 (m), 323 (m) cm⁻¹. Field desorption mass spectrum m/e for parent W₂ S₈ C₁₀ H₂₀ N₂, relative abundance (calc., exp.): 788 (21,21); 789 (26,24); 790 (66,68); 791 (46,43); 792 (100,100); 793 (52,60); 794 (89,79); 795 (26,32); 796 (50,41).

EXAMPLE 3 Production of W₂ S₄ (S₂ CN(i-C₄ H₉)₂)₂

The procedure of Example 2 was repeated using Na(S₂ CN(i-C₄ H₉)₂) instead of the diethyl analog. The resulting product had characteristic IR bands at 535, 523, 448, 372 and 328 cm⁻¹ (all ±5 cm⁻¹).

EXAMPLE 4 Production of (Et₂ NCS₂)₂ (MeCN)₂ W₂ (μ³ -S)₄ Co₂ (CO)₂

In an inert atmosphere glove box, solid Co₂ (CO)₈ (0.505 g, 1.48 mmol) was added over a period of five minutes to a stirred orange slurry of W₂ S₄ (S₂ CNEt₂)₂ (1.175 g, 1.49 mmol) in 80 ml acetonitrile as made according to Example 2. The solution darkened to a brown-black slurry as gas was evolved. The mixture was stirred 2 hours and then filtered. The filtrate was concentrated to ca. 60 ml and placed in a -10° freezer overnight. Black crystalline (Et₂ NCS₂)₂ (MeCN)₂ W₂ (μ³ -S)₄ Co₂ (CO)₂ was filtered from the dark solution on a sintered-glass Schlenk filter, washed with 8 mL acetonitrile, and dried in vacuo. Yield was 650 mg (42%).

Anal. Calcd. for C₁₆ H₂₆ N₄ O₂ S₈ Co₂ W₂ : C, 18.33; H, 2.50; N, 5.34; W, 35.07. Found: C, 18.03; H, 2.49; N, 5.27; W, 35.27. IR (KBr pellet): 1961 (s), 1938 (s), 1505 (s), 1456 (w), 14.36 (m), 1358 (w), 1300 (w), 1273 (m), 1209 (m), 1147 (m), 1095 (w), 1075 (m), 915 (w), 847 (w), 783 (w), 521 (m), 394 (w), and 368 (w) cm⁻¹.

EXAMPLE 5 Production of (Et₂ NCS₂)₂ (MeCN)₂ Mo₂ (μ³ -S)₄ Co₂ (CO)₂

In an inert atmosphere glove box, solid Co₂ (CO)₈ (sublimed, 0.111 g, 0.324 mmoles) was added over a period of several minutes to a stirred slurry of red-brown Mo₂ S₄ (S₂ CNEt₂)₂ (0.200 g, 0.324 mmoles) in 20 ml dry CH₃ CN (distilled from CaH₂). This material was made via the process disclosed in Miller et al, J. Am. Chem. Soc. (1980), pp. 5104-5106. The solution darkened rapidly with gentle evolution of carbon monoxide. After stirring for two hours, the solution was filtered and the dark black-brown filtrate was concentrated under vacuum to a volume of 5 ml. The mixture was then allowed to stand 18 hours. Black crystalline (Et₂ NCS₂)₂ (MeCN)₂ Mo₂ (μ³ -S)₄ Co₂ (CO)₂ was filtered on a medium porosity sintered glass frit, and dried in vacuo. Yield was 200 mg (71%).

IR spectrum (KBr pellet): 1983 (s), 1960 (s), 1505 (s), 1465 (m), 1442 (m), 1385 (w), 1368 (m), 1310 (w), 1280 (s), 1220 (m), 1152 (m), 1103 (w), 1083 (m), 1008 (w), 976 (w), 922 (w), 851 (w), 790 (w), 578 (w), 521 (m), 498 (w), 436 (vw), 401 (w), 371 (m). Anal. Calcd. for C₁₆ H₂₆ N₄ O₂ S₈ Co₂ Mo₂ : C, 22.02; H, 3.00; N, 6.42; l Mo, 21.99; Co, 13.51. Found C, 18.59; H, 2.83; N, 5.11; Mo, 21.10; Co, 14.22.

A single crystal x-ray diffraction study was carried out on the product. The structure is illustrated in FIG. 1 and the x-ray structure factors are given in Table 1. The molecule contains a Co₂ Mo₂ (μ₃ -S)₄ core. The four metal atoms are joined by six metal-metal bonds forming an approximate tetrahedron of C_(2v) symmetry. Each triangular face of the tetrahedron is capped by a sulfur, to form the overall "thiocubane" core. Each cobalt is further bonded to a single terminal CO. The coordination environment about the cobalt atoms (discounting the M-M bonds) very nearly tetrahedral. Each molybdenum atom is bound to tow dithiocarbamate sulfur atoms and to the nitrogen of an acetonitrile molecule, in addition to three capping "μ³ -S" atoms. The coordination environment about the molybdenum atoms is distorted octahedral. The molecule resides on a crystallographic C₂ axis which bisects the Mo-Mo' and Co-Co' bonds.

                  TABLE 1                                                          ______________________________________                                         MO2CO2S4(CO)2(NCCH3)2[S2CH(C2H5)2]2                                            H    K     L     FOBS  FCAL  H    K    L   FOBS  FCAL                          ______________________________________                                         2    0     0     4951  4967  20   4    0   202   192                           4    0     0     1638  1654  24   4    0   295   289                           6    0     0     2661  2633  1    5    0   2267  2247                          8    0     0     5917  5956  3    5    0   2207  2178                          10   0     0     4832  4831  5    5    0   206   190                           12   0     0     2120  2099  7    5    0   1914  1887                          14   0     0     641   656   9    5    0   1668  1658                          16   0     0     679   675   11   5    0   1846  1841                          18   0     0     1518  1511  13   5    0   674   685                           20   0     0     1127  1119  15   5    0   212   102                           22   0     0     637   626   17   5    0   776   776                           24   0     0     566   543   19   5    0   728   719                           1    1     0     1089  1082  21   5    0   623   623                           3    1     0     968   959   23   5    0   217   231                           5    1     0     793   797   0    6    0   3088  3042                          7    1     0     604   618   2    6    0   2843  2796                          9    1     0     1777  1775  4    6    0   362   366                           11   1     0     476   462   6    6    0   668   675                           13   1     0     187   206   8    6    0   1851  1839                          15   1     0     451   439   10   6    0   2127  2112                          17   1     0     274   263   12   6    0   1091  1107                          19   1     0     520   526   14   6    0   489   491                           27   1     0     244   222   18   6    0   692   707                           0    2     0     1656  1650  20   6    0   564   558                           2    2     0     2666  2658  22   6    0   574   579                           4    2     0     836   829   24   6    0   502   504                           6    2     0     344   349   1    7    0   150   102                           8    2     0     1955  1974  3    7    0   802   807                           10   2     0     1651  1632  5    7    0   599   596                           12   2     0     827   802   7    7    0   320   314                           14   2     0     289   294   9    7    0   316   307                           16   2     0     115   126   11   7    0   643   668                           18   2     0     590   594   13   7    0   1342  1364                          20   2     0     503   490   15   7    0   258   264                           22   2     0     353   349   17   7    0   527   523                           24   2     0     268   278   21   7    0   486   484                           1    3     0     3046  3044  23   7    0   268   269                           3    3     0     974   932   0    8    0   192   184                           5    3     0     828   811   2    8    0   333   309                           7    3     0     1481  1509  4    8    0   510   526                           9    3     0     1836  1815  6    8    0   609   595                           11   3     0     353   338   8    8    0   292   272                           13   3     0     730   726   10   8    0   226   188                           15   3     0     479   461   12   8    0   746   752                           17   3     0     935   926   14   8    0   132   145                           19   3     0     708   713   16   8    0   327   335                           23   3     0     129   139   18   8    0   283   277                           0    4     0     4682  4724  20   8    0   563   562                           2    4     0     1863  1869  22   8    0   476   470                           4    4     0     662   642   1    9    0   1706  1695                          6    4     0     359   349   3    9    0   998   989                           8    4     0     2656  2596  5    9    0   404   409                           10   4     0     2096  2117  7    9    0   1276  1284                          12   4     0     346   339   9    9    0   1452  1431                          14   4     0     259   263   11   9    0   884   873                           18   4     0     622   612   13   9    0   164   185                           15   9     0     562   566   -10  2    1   1180  1147                          17   9     0     655   670   -8   2    1   811   801                           19   9     0     490   496   -6   2    1   1215  1254                          0    10    0     820   824   -4   2    1   1016  972                           2    10    0     451   473   -2   2    1   2168  2199                          8    10    0     260   267   0    2    1   477   460                           10   10    0     291   312   2    2    1   2305  2244                          14   10    0     248   267   4    2    1   659   649                           16   10    0     272   298   6    2    1   860   891                           1    11    0     1141  1134  8    2    1   981   1021                          3    11    0     1036  1046  10   2    1   174   188                           5    11    0     182   179   12   2    1   387   395                           7    11    0     629   642   16   2    1   675   654                           9    11    0     604   610   18   2    1   1529  1476                          11   11    0     1066  1064  20   2    1   586   574                           13   11    0     1007  1006  22   2    1   517   493                           15   11    0     177   200   26   2    1   807   757                           0    12    0     399   406   -23  3    1   210   219                           2    12    0     372   397   -19  3    1   383   356                           4    12    0     214   239   -17  3    1   395   391                           6    12    0     372   360   -13  3    1   241   224                           8    12    0     429   453   -11  3    1   623   614                           10   12    0     314   295   -9   3    1   1252  1209                          12   12    0     349   360   -7   3    1   111   104                           1    13    0     210   216   -5   3    1   740   733                           3    13    0     317   317   -3   3    1   618   611                           5    13    0     249   260   -1   3    1   2024  1997                          9    13    0     193   207   1    3    1   221   231                           -25  1     1     348   338   3    3    1   267   254                           -23  1     1     389   394   5    3    1   440   431                           -21  1     1     666   676   7    3    1   443   433                           -19  1     1     1170  1178  11   3    1   306   317                           -17  1     1     696   695   13   3    1   210   220                           -15  1     1     515   525   15   3    1   448   444                           -13  1     1     1186  1211  17   3    1   232   246                           -11  1     1     3331  3248  19   3    1   305   288                           -9   1     1     3748  3860  21   3    1   442   428                           -7   1     1     706   706   25   3    1   160   128                           -5   1     1     465   472   -22  4    1   266   275                           -3   1     1     3777  3637  -20  4    1   569   598                           -1   1     1     5915  5903  -18  4    1   675   677                           1    1     1     2840  2847  -14  4    1   434   436                           3    1     1     1779  1770  -12  4    1   1238  1250                          7    1     1     2125  2096  -10  4    1   1678  1694                          9    1     1     2700  2710  -8   4    1   1310  1254                          11   1     1     1511  1547  -6   4    1   204   236                           13   1     1     939   974   -4   4    1   2233  2150                          15   1     1     487   497   -2   4    1   3028  3001                          17   1     1     963   953   0    4    1   2891  2844                          19   1     1     958   934   2    4    1   612   591                           21   1     1     574   576   4    4    1   1443  1429                          23   1     1     616   585   6    4    1   1894  1888                          -22  2     1     467   475   8    4    1   2844  2821                          -18  2     1     241   272   10   4    1   1548  1543                          -14  2     1     487   519   14   4    1   368   360                           -12  2     1     674   663   16   4    1   1436  1410                          18   4     1     1198  1175  -7   7    1   659   674                           20   4     1     873   860   -5   7    1   583   576                           22   4     1     358   361   -3   7    1   1042  1052                          24   4     1     284   250   -1   7    1   1219  1194                          -25  5     1     349   351   1    7    1   1211  1194                          -23  5     1     262   252   3    7    1   659   661                           -21  5     1     392   383   5    7    1   530   517                           -19  5     1     933   954   7    7    1   804   780                           -17  5     1     458   471   9    7    1   1433  1392                          -13  5     1     1029  1032  11   7    1   1079  1061                          -11  5     1     2675  2685  13   7    1   523   529                           -9   5     1     3071  3038  15   7    1   241   251                           -7   5     1     698   718   17   7    1   618   599                           -5   5     1     440   460   19   7    1   825   793                           -3   5     1     2203  2228  21   7    1   869   836                           -1   5     1     3894  3899  23   7    1   201   211                           1    5     1     2799  2787  -22  8    1   404   441                           3    5     1     443   452   -18  8    1   331   349                           5    5     1     533   513   -16  8    1   476   500                           7    5     1     1367  1332  -14  8    1   479   531                           9    5     1     1937  1932  -10  8    1   617   610                           11   5     1     920   911   -8   8    1   346   336                           13   5     1     1336  1312  -6   8    1   186   184                           15   5     1     658   660   -4   8    1   368   373                           17   5     1     706   688   -2   8    1   457   444                           19   5     1     609   588   0    8    1   524   514                           21   5     1     514   506   2    8    1   552   553                           23   5     1     571   541   4    8    1   936   943                           -24  6     1     406   423   6    8    1   468   486                           -22  6     1     710   741   8    8    1   901   884                           -20  6     1     504   528   12   8    1   325   305                           -18  6     1     177   177   14   8    1   285   271                           -14  6     1     992   1032  16   8    1   743   718                           -12  6     1     1412  1521  18   8    1   597   508                           -10  6     1     1189  1170  20   8    1   184   162                           -8   6     1     1064  1108  -15  9    1   203   205                           -6   6     1     211   232   -13  9    1   513   541                           -4   6     1     1519  1517  -7   9    1   346   331                           -2   6     1     1516  1516  -5   9    1   593   593                           0    6     1     1527  1482  -3   9    1   834   827                           2    6     1     2328  2331  3    9    1   191   172                           6    6     1     981   956   5    9    1   1430  1420                          8    6     1     625   617   7    9    1   939   917                           10   6     1     1291  1252  9    9    1   417   379                           12   6     1     1108  1082  11   9    1   591   591                           14   6     1     278   281   13   9    1   614   603                           16   6     1     212   193   15   9    1   1013  1017                          18   6     1     185   195   17   9    1   658   645                           20   6     1     308   328   19   9    1   629   613                           -23  7     1     430   418   -18  10   1   303   315                           -21  7     1     386   403   -14  10   1   718   735                           -19  7     1     228   254   -12  10   1   1051  1037                          -15  7     1     434   468   -10  10   1   1014  1007                          -13  7     1     668   701   -8   10   1   976   907                           -11  7     1     663   727   -6   10   1   187   167                           -9   7     1     550   562   -4   10   1   1017  1044                          -2   10    1     1554  1571  8    0    2   3478  3537                          0    10    1     1399  1407  10   0    2   1197  1186                          2    10    1     1325  1328  12   0    2   858   872                           6    10    1     1119  1107  14   0    2   617   614                           8    10    1     999   1005  16   0    2   1730  1681                          10   10    1     1316  1312  18   0    2   1023  1011                          12   10    1     723   740   20   0    2   374   366                           14   10    1     276   258   22   0    2   271   297                           16   10    1     449   441   24   0    2   446   448                           18   10    1     548   549   26   0    2   725   724                           -11  11    1     251   281   -25  1    2   267   280                           -9   11    1     414   441   -19  1    2   312   296                           -7   11    1     307   299   -17  1    2   675   672                           -1   11    1     352   378   -15  1    2   607   590                           1    11    1     517   503   -11  1    2   191   133                           3    11    1     456   466   -9   1    2   1751  1795                          5    11    1     203   194   -7   1    2   987   1033                          9    11    1     200   236   -5   1    2   553   555                           11   11    1     497   510   -3   1    2   1603  1623                          13   11    1     509   499   -1   1    2   398   390                           15   11    1     187   208   1    1    2   814   777                           -12  12    1     774   752   3    1    2   2183  2185                          -10  12    1     381   373   5    1    2   434   429                           -8   12    1     236   236   7    1    2   1374  1382                          -4   12    1     419   425   9    1    2   895   900                           -2   12    1     485   499   11   1    2   537   562                           0    12    1     622   630   13   1    2   285   292                           2    12    1     885   890   15   1    2   647   649                           4    12    1     437   445   17   1    2   1746  1711                          8    12    1     251   274   19   1    2   685   685                           10   12    1     772   763   21   1    2   638   625                           12   12    1     721   725   25   1    2   748   709                           -9   13    1     263   288   -26  2    2   279   301                           -5   13    1     279   313   -24  2    2   373   380                           -3   13    1     680   707   -22  2    2   311   306                           -1   13    1     425   441   -20  2    2   282   280                           1    13    1     436   428   -16  2    2   365   364                           5    13    1     704   711   -14  2    2   896   881                           7    13    1     782   782   -12  2    2   753   762                           9    13    1     556   571   -10  2    2   760   713                           -26  0     2     434   421   -8   2    2   152   108                           -24  0     2     817   822   -4   2    2   1313  1356                          -22  0     2     1096  1107  -2   2    2   1413  1419                          -20  0     2     1591  1569  0    2    2   1573  1560                          -18  0     2     592   595   2    2    2   1180  1176                          -16  0     2     1418  1397  4    2    2   494   467                           -14  0     2     1816  1784  6    2    2   450   466                           -12  0     2     4108  4013  8    2    2   823   831                           -10  0     2     2924  2818  10   2    2   863   864                           -8   0     2     353   381   12   2    2   866   871                           -6   0     2     2451  2405  14   2    2   145   125                           -4   0     2     3143  3043  16   2    2   494   484                           -2   0     2     4371  4488  18   2    2   778   759                           0    0     2     2190  2190  20   2    2   516   503                           2    0     2     2088  2068  22   2    2   163   175                           6    0     2     1789  1769  24   2    2   228   211                           26   2     2     367   333   -1   5    2   2346  2353                          -25  3     2     277   297   1    5    2   655   661                           -17  3     2     1061  1079  3    5    2   653   648                           -15  3     2     860   876   5    5    2   1455  1442                          -13  3     2     435   426   7    5    2   1493  1475                          -11  3     2     299   276   9    5    2   1106  1105                          -9   3     2     1479  1375  11   5    2   561   560                           -7   3     2     2320  2464  13   5    2   604   595                           -5   3     2     1495  1466  15   5    2   1004  900                           -3   3     2     558   570   17   5    2   452   437                           -1   3     2     137   148   19   5    2   693   602                           1    3     2     1268  1225  23   5    2   331   333                           3    3     2     288   314   -24  6    2   467   463                           5    3     2     900   903   -22  6    2   439   430                           7    3     2     2724  2737  -20  6    2   478   489                           9    3     2     1623  1622  -16  6    2   580   609                           11   3     2     441   464   -14  6    2   760   819                           13   3     2     297   284   -12  6    2   831   896                           15   3     2     1551  1502  -10  6    2   1085  1119                          17   3     2     2237  2182  -8   6    2   154   108                           19   3     2     1362  1324  -6   6    2   222   189                           21   3     2     656   641   -4   6    2   509   511                           25   3     2     1024  980   -2   6    2   946   953                           -24  4     2     226   235   0    6    2   1542  1527                          -22  4     2     378   371   2    6    2   706   703                           -20  4     2     850   876   4    6    2   1466  1466                          -18  4     2     605   623   6    6    2   541   523                           -16  4     2     243   212   8    6    2   1252  1221                          -14  4     2     445   419   10   6    2   1233  1211                          -12  4     2     1578  1551  12   6    2   1506  1480                          -10  4     2     1672  1643  14   6    2   251   280                           -8   4     2     423   418   16   6    2   606   573                           -6   4     2     753   751   18   6    2   1043  1028                          -2   4     2     2151  2127  20   6    2   786   759                           0    4     2     564   560   22   6    2   323   316                           2    4     2     858   826   -23  7    2   370   381                           4    4     2     1584  1554  -21  7    2   328   331                           6    4     2     774   766   -17  7    2   346   353                           8    4     2     529   523   -13  7    2   352   360                           10   4     2     261   265   -11  7    2   435   447                           12   4     2     865   863   -9   7    2   1014  1042                          14   4     2     1066  1029  -7   7    2   1403  1444                          16   4     2     241   239   -3   7    2   216   234                           20   4     2     179   168   -1   7    2   273   280                           22   4     2     322   298   1    7    2   1849  1856                          -25  5     2     338   347   3    7    2   448   447                           -23  5     2     573   571   5    7    2   225   196                           -21  5     2     514   526   7    7    2   661   658                           -19  5     2     297   301   11   7    2   238   229                           -15  5     2     763   780   13   7    2   156   134                           -13  5     2     1611  1586  15   7    2   674   664                           -11  5     2     1126  1121  17   7    2   781   758                           -9   5     2     956   936   19   7    2   440   398                           -7   5     2     216   207   21   7    2   173   132                           -5   5     2     1635  1694  -22  8    2   171   168                           -3   5     2     1705  1749  -20  8    2   268   255                           -18  8     2     369   385   -11  11   2   620   618                           -16  8     2     408   423   -9   11   2   510   494                           -14  8     2     477   519   -7   11   2   297   304                           -12  8     2     263   239   -5   11   2   514   535                           -10  8     2     486   467   -3   11   2   676   699                           -8   8     2     249   213   -1   11   2   715   732                           -6   8     2     954   925   1    11   2   1112  1124                          -4   8     2     945   930   3    11   2   258   276                           -2   8     2     379   374   5    11   2   411   416                           0    8     2     490   493   7    11   2   356   354                           4    8     2     1350  1324  9    11   2   762   783                           6    8     2     1093  1073  11   11   2   538   554                           8    8     2     1065  1056  13   11   2   151   73                            10   8     2     1017  1025  -4   12   2   221   262                           12   8     2     179   148   0    12   2   212   243                           14   8     2     812   811   2    12   2   191   212                           16   8     2     783   784   4    12   2   274   270                           18   8     2     831   826   6    12   2   178   155                           20   8     2     741   710   8    12   2   330   340                           -21  9     2     272   277   10   12   2   577   582                           -17  9     2     219   211   12   12   2   180   170                           -15  9     2     552   598   -9   13   2   248   226                           -13  9     2     671   683   -5   13   2   283   272                           -11  9     2     681   650   -3   13   2   439   460                           -9   9     2     227   232   -1   13   2   422   408                           -7   9     2     509   506   1    13   2   199   205                           -5   9     2     1138  1150  5    13   2   183   233                           -3   9     2     1134  1146  7    13   2   218   243                           -1   9     2     827   832   -27  1    3   436   451                           1    9     2     255   242   -25  1    3   783   770                           3    9     2     724   702   -23  1    3   654   644                           5    9     2     913   926   -21  1    3   626   622                           7    9     2     1121  1109  -17  1    3   1004  1061                          9    9     2     782   771   -15  1    3   951   961                           11   9     2     420   409   -13  1    3   943   904                           13   9     2     395   373   -11  1    3   723   699                           15   9     2     733   716   -9   1    3   353   341                           17   9     2     820   793   -7   1    3   237   287                           19   9     2     582   578   -5   1    3   747   682                           -14  10    2     254   248   -3   1    3   671   710                           -10  10    2     264   239   -1   1    3   1082  1117                          -8   10    2     194   223   1    1    3   543   529                           -6   10    2     584   618   3    1    3   1887  1846                          -4   10    2     1085  1096  5    1    3   134   143                           -2   10    2     371   334   7    1    3   1258  1261                          0    10    2     176   151   9    1    3   373   367                           2    10    2     751   756   11   1    3   409   404                           4    10    2     1594  1595  15   1    3   1038  1049                          6    10    2     1032  1032  17   1    3   439   441                           8    10    2     230   240   23   1    3   393   391                           10   10    2     252   251   25   1    3   444   426                           12   10    2     864   850   -26  2    3   724   696                           14   10    2     900   876   -24  2    3   149   187                           16   10    2     333   348   -22  2    3   370   387                           -15  11    2     546   509   -20  2    3   829   822                           -13  11    2     799   778   -18  2    3   1804  1859                          -16  2     3     1418  1403  10   4    3   567   570                           -14  2     3     195   202   12   4    3   782   779                           -12  2     3     1050  1008  14   4    3   1446  1425                          -10  2     3     2267  2126  16   4    3   1572  1556                          -8   2     3     2458  2356  18   4    3   931   931                           -6   2     3     595   631   22   4    3   219   202                           -2   2     3     324   323   24   4    3   654   616                           0    2     3     803   797   -25  5    3   610   616                           2    2     3     101   107   -23  5    3   422   428                           4    2     3     140   162   -21  5    3   558   502                           6    2     3     2646  2666  -19  5    3   197   155                           8    2     3     2329  2354  -17  5    3   777   829                           10   2     3     834   853   -15  5    3   457   481                           12   2     3     704   709   -13  5    3   171   160                           14   2     3     1288  1274  -11  5    3   486   492                           16   2     3     2250  2213  -9   5    3   165   178                           18   2     3     1159  1125  -7   5    3   419   447                           20   2     3     889   880   -5   5    3   712   723                           22   2     3     143   132   -3   5    3   283   275                           24   2     3     777   741   -1   5    3   165   131                           -21  3     3     370   351   1    5    3   606   608                           -19  3     3     524   541   3    5    3   1573  1584                          -17  3     3     193   148   5    5    3   398   410                           -15  3     3     291   285   7    5    3   438   431                           -13  3     3     341   330   9    5    3   169   169                           -11  3     3     395   390   11   5    3   367   358                           -9   3     3     166   140   13   5    3   411   388                           -7   3     3     660   643   15   5    3   367   330                           -5   3     3     754   755   17   5    3   323   284                           -3   3     3     982   939   19   5    3   257   244                           3    3     3     941   941   23   5    3   238   219                           5    3     3     1319  1307  -24  6    3   386   394                           7    3     3     319   343   -22  6    3   594   608                           9    3     3     944   935   -20  6    3   251   252                           13   3     3     663   654   -18  6    3   343   352                           17   3     3     779   769   -16  6    3   176   217                           19   3     3     593   591   -14  6    3   906   970                           25   3     3     224   229   -12  6    3   674   734                           -26  4     3     664   657   -10  6    3   1084  1113                          -24  4     3     560   555   -8   6    3   503   541                           -22  4     3     249   237   -6   6    3   854   870                           -20  4     3     320   352   -4   6    3   1210  1212                          -18  4     3     1169  1216  -2   6    3   601   610                           -16  4     3     1515  1588  0    6    3   334   335                           -14  4     3     1252  1273  2    6    3   700   680                           -12  4     3     459   467   4    6    3   857   849                           -10  4     3     1066  1048  8    6    3   484   486                           -8   4     3     2465  2499  10   6    3   312   209                           -6   4     3     2067  2172  12   6    3   956   939                           -4   4     3     1435  1484  16   6    3   520   522                           -2   4     3     1332  1311  18   6    3   176   139                           0    4     3     1023  1009  20   6    3   316   275                           2    4     3     928   949   22   6    3   355   354                           4    4     3     2318  2358  -23  7    3   245   274                           6    4     3     2262  2294  -21  7    3   173   186                           8    4     3     1473  1477  -19  7    3   546   575                           -17  7     3     655   706   19   9    3   462   452                           -15  7     3     628   655   -18  10   3   280   306                           -13  7     3     334   354   -16  10   3   568   603                           -11  7     3     385   405   -14  10   3   910   906                           -9   7     3     672   650   -12  10   3   517   506                           -7   7     3     966   976   -8   10   3   402   406                           -5   7     3     191   161   -6   10   3   907   909                           -3   7     3     364   373   -4   10   3   751   762                           -1   7     3     201   185   -2   10   3   477   495                           1    7     3     176   195   0    10   3   307   301                           3    7     3     243   194   2    10   3   441   442                           5    7     3     670   668   4    10   3   757   775                           7    7     3     753   751   6    10   3   528   511                           9    7     3     1097  1103  8    10   3   503   517                           11   7     3     448   432   12   10   3   392   393                           13   7     3     428   398   14   10   3   517   514                           15   7     3     705   687   16   10   3   358   367                           17   7     3     961   938   -13  11   3   329   304                           19   7     3     670   648   -11  11   3   323   280                           -20  8     3     278   297   -7   11   3   369   344                           -18  8     3     734   780   -5   11   3   675   671                           -16  8     3     683   726   -3   11   3   427   436                           -12  8     3     307   291   1    11   3   395   401                           -10  8     3     733   713   3    11   3   733   741                           -8   8     3     1142  1086  5    11   3   549   551                           -6   8     3     493   476   9    11   3   313   327                           -4   8     3     400   399   11   11   3   425   416                           -2   8     3     270   257   13   11   3   327   305                           0    8     3     477   479   -12  12   3   352   338                           2    8     3     393   400   -10  12   3   365   363                           4    8     3     442   436   -8   12   3   402   396                           6    8     3     1097  1097  -6   12   3   223   241                           8    8     3     637   626   -4   12   3   386   402                           10   8     3     274   265   -2   12   3   287   290                           12   8     3     217   223   0    12   3   429   415                           14   8     3     454   451   4    12   3   277   264                           16   8     3     784   767   -9   13   3   486   477                           18   8     3     428   419   -7   13   3   754   791                           -19  9     3     396   428   -5   13   3   1027  1041                          -17  9     3     469   511   -3   13   3   460   474                           -15  9     3     844   902   1    13   3   373   377                           -13  9     3     578   562   3    13   3   1004  1018                          -9   9     3     551   523   5    13   3   894   913                           -7   9     3     1508  1471  7    13   3   560   579                           -5   9     3     2289  2238  -26  0    4   1011  1014                          -3   9     3     1079  1073  -24  0    4   501   487                           -1   9     3     249   246   -22  0    4   199   208                           1    9     3     996   1002  -20  0    4   362   359                           3    9     3     2211  2186  -18  0    4   1578  1665                          5    9     3     1847  1850  -16  0    4   837   831                           7    9     3     983   966   -14  0    4   526   503                           9    9     3     353   327   -12  0    4   244   191                           11   9     3     641   646   -10  0    4   1393  1314                          13   9     3     1146  1118  -8   0    4   2112  1974                          15   9     3     721   723   -6   0    4   287   285                           17   9     3     595   589   -4   0    4   1728  1677                          -2   0     4     1710  1730  16   2    4   336   365                           0    0     4     3242  3238  18   2    4   207   203                           2    0     4     2649  2604  22   2    4   271   273                           4    0     4     1046  1052  24   2    4   233   244                           6    0     4     311   297   -25  3    4   570   550                           8    0     4     1879  1874  -23  3    4   240   223                           10   0     4     2235  2295  -21  3    4   782   796                           12   0     4     1325  1341  -19  3    4   1786  1827                          14   0     4     1326  1345  -17  3    4   1763  1855                          16   0     4     554   565   -15  3    4   684   660                           18   0     4     1028  1038  -11  3    4   1314  1275                          20   0     4     886   879   -9   3    4   2478  2459                          22   0     4     482   491   -7   3    4   1847  1906                          24   0     4     426   419   -5   3    4   1948  2045                          -27  1     4     654   644   -3   3    4   2037  2003                          -25  1     4     214   235   -1   3    4   400   405                           -23  1     4     239   232   1    3    4   1837  1802                          -21  1     4     571   570   3    3    4   2064  2121                          -19  1     4     1249  1277  5    3    4   2581  2600                          -17  1     4     1156  1214  7    3    4   2173  2211                          -13  1     4     241   258   9    3    4   248   108                           -11  1     4     823   779   11   3    4   388   387                           -9   1     4     1926  1835  13   3    4   1358  1363                          -7   1     4     1006  1024  15   3    4   1596  1596                          -5   1     4     1002  994   17   3    4   567   580                           -3   1     4     556   555   19   3    4   316   313                           -1   1     4     903   884   23   3    4   422   420                           1    1     4     849   814   -26  4    4   365   376                           3    1     4     960   936   -22  4    4   351   353                           5    1     4     3286  3229  -20  4    4   162   143                           7    1     4     1171  1207  -18  4    4   409   422                           9    1     4     171   176   -16  4    4   246   251                           11   1     4     219   200   -14  4    4   389   357                           13   1     4     807   816   -12  4    4   265   235                           15   1     4     1096  1083  -10  4    4   159   121                           17   1     4     447   442   -8   4    4   207   196                           19   1     4     347   344   -6   4    4   1067  1113                          23   1     4     241   236   -4   4    4   674   663                           25   1     4     301   311   -2   4    4   204   206                           -26  2     4     361   370   0    4    4   415   410                           -24  2     4     241   229   2    4    4   317   318                           -20  2     4     490   504   4    4    4   345   348                           -18  2     4     665   693   6    4    4   124   154                           -16  2     4     517   536   8    4    4   1695  1706                          -10  2     4     1005  942   10   4    4   1052  1086                          -8   2     4     608   582   12   4    4   185   151                           -6   2     4     444   450   16   4    4   827   808                           -4   2     4     370   363   18   4    4   1036  1004                          -2   2     4     315   294   20   4    4   359   356                           2    2     4     746   736   -25  5    4   539   527                           4    2     4     924   933   -23  5    4   457   475                           6    2     4     616   649   -19  5    4   495   504                           8    2     4     252   265   -17  5    4   902   944                           10   2     4     671   659   -15  5    4   1028  1106                          12   2     4     547   534   -13  5    4   467   501                           14   2     4     388   383   -11  5    4   251   197                           -9   5     4     1155  1175  -20  8    4   564   592                           -7   5     4     1582  1654  -18  8    4   672   715                           -5   5     4     1485  1518  -16  8    4   805   845                           -3   5     4     275   262   -14  8    4   548   588                           -1   5     4     756   769   -12  8    4   274   295                           1    5     4     1040  1061  -10  8    4   639   631                           3    5     4     2138  2161  -8   8    4   1300  1260                          5    5     4     653   633   -6   8    4   1614  1577                          7    5     4     216   199   -4   8    4   1078  1048                          9    5     4     753   781   -2   8    4   134   59                            11   5     4     1237  1196  0    8    4   291   290                           13   5     4     718   710   2    8    4   1247  1232                          15   5     4     401   383   4    8    4   1430  1423                          19   5     4     349   333   6    8    4   946   944                           21   5     4     392   363   8    8    4   905   899                           23   5     4     300   309   10   8    4   159   60                            -24  6     4     234   243   12   8    4   639   625                           -20  6     4     545   570   14   8    4   815   804                           -18  6     4     683   715   16   8    4   808   808                           -16  6     4     429   472   18   8    4   778   754                           -14  6     4     188   210   -19  9    4   637   698                           -12  6     4     191   178   -17  9    4   899   958                           -10  6     4     840   873   -15  9    4   728   782                           -8   6     4     289   295   -13  9    4   235   242                           -4   6     4     176   131   -11  9    4   564   555                           0    6     4     586   589   -9   9    4   1310  1260                          2    6     4     487   484   -7   9    4   1143  1113                          4    6     4     454   446   -5   9    4   1011  992                           6    6     4     478   467   -3   9    4   289   309                           8    6     4     168   119   -1   9    4   537   516                           10   6     4     706   701   1    9    4   1152  1148                          12   6     4     569   552   3    9    4   1159  1170                          14   6     4     594   574   5    9    4   940   935                           16   6     4     392   376   9    9    4   458   446                           18   6     4     302   315   11   9    4   773   777                           22   6     4     367   344   13   9    4   527   535                           -23  7     4     242   234   15   9    4   285   276                           -21  7     4     350   371   -16  10   4   610   608                           -19  7     4     863   907   -14  10   4   728   713                           -17  7     4     648   701   -10  10   4   267   236                           -13  7     4     306   312   -8   10   4   820   810                           -11  7     4     531   466   -6   10   4   1391  1367                          -9   7     4     1086  1044  -4   10   4   732   725                           -7   7     4     628   641   -2   10   4   221   248                           - 5  7     4     355   348   0    10   4   188   174                           -3   7     4     797   796   2    10   4   1043  1045                          -1   7     4     276   282   4    10   4   917   932                           1    7     4     339   323   6    10   4   565   561                           3    7     4     643   647   8    10   4   358   338                           5    7     4     1011  1018  12   10   4   432   450                           7    7     4     924   924   14   10   4   312   299                           11   7     4     169   167   16   10   4   324   298                           13   7     4     239   212   -15  11   4   419   426                           15   7     4     539   518   -7   11   4   474   471                           21   7     4     412   380   -5   11   4   319   321                           -22  8     4     222   253   -3   11   4   254   243                           -1   11    4     198   199   12   2    5   592   593                           1    11    4     354   347   14   2    5   845   816                           3    11    4     379   384   16   2    5   412   425                           7    11    4     145   132   18   2    5   239   231                           11   11    4     317   337   20   2    5   405   389                           13   11    4     387   382   24   2    5   332   329                           -12  12    4     285   280   -23  3    5   235   206                           -10  12    4     411   424   -21  3    5   363   359                           -8   12    4     377   403   -17  3    5   468   499                           -6   12    4     336   343   -15  3    5   361   373                           0    12    4     157   146   -13  3    5   228   197                           2    12    4     342   356   -11  3    5   460   420                           4    12    4     361   357   -9   3    5   250   241                           6    12    4     255   282   -7   3    5   487   518                           3    13    4     239   241   -5   3    5   663   660                           -27  1     5     458   443   -3   3    5   299   309                           -23  1     5     145   66    -1   3    5   1054  1068                          -21  1     5     163   180   1    3    5   158   159                           -19  1     5     839   843   3    3    5   579   586                           -17  1     5     341   357   5    3    5   972   969                           -13  1     5     178   163   7    3    5   1186  1206                          -11  1     5     919   880   9    3    5   660   690                           -9   1     5     1814  1734  13   3    5   560   562                           -7   1     5     1547  1517  15   3    5   693   685                           -5   1     5     527   554   17   3    5   520   498                           -3   1     5     419   396   19   3    5   154   146                           -1   1     5     3525  3398  21   3    5   296   283                           1    1     5     3236  3142  -26  4    5   543   544                           3    1     5     1492  1488  -22  4    5   375   379                           5    1     5     296   300   -20  4    5   986   1015                          7    1     5     2297  2323  -18  4    5   1429  1508                          9    1     5     2544  2617  -16  4    5   937   989                           11   1     5     1554  1575  -14  4    5   653   671                           13   1     5     766   761   -12  4    5   413   421                           15   1     5     332   313   -10  4    5   1771  1790                          17   1     5     910   913   -8   4    5   2645  2713                          19   1     5     700   691   -6   4    5   2404  2468                          21   1     5     439   419   -4   4    5   1272  1300                          23   1     5     446   458   -2   4    5   1264  1274                          -26  2     5     245   239   0    4    5   2838  2911                          -24  2     5     233   241   2    4    5   2500  2535                          -22  2     5     221   201   4    4    5   1859  1911                          -20  2     5     1045  1053  6    4    5   369   360                           -18  2     5     1178  1191  8    4    5   1328  1349                          -16  2     5     628   645   10   4    5   1213  1244                          -14  2     5     885   860   12   4    5   1001  975                           -12  2     5     323   314   14   4    5   603   591                           -10  2     5     1435  1424  18   4    5   226   195                           -8   2     5     2004  1967  20   4    5   254   242                           -6   2     5     2069  2103  22   4    5   315   326                           -4   2     5     2840  2720  -19  5    5   329   364                           -2   2     5     1091  1031  -15  5    5   261   277                           0    2     5     1759  1725  -11  5    5   854   892                           2    2     5     1698  1729  -9   5    5   1115  1162                          4    2     5     2610  2654  -3   5    5   753   771                           6    2     5     1645  1695  -1   5    5   2333  2366                          1    5     5     1869  1902  -6   8    5   1322  1299                          3    5     5     611   595   -4   8    5   1082  1060                          7    5     5     2012  2032  0    8    5   1018  1018                          9    5     5     2045  2065  2    8    5   1002  979                           11   5     5     1073  1074  4    8    5   979   977                           13   5     5     466   440   6    8    5   233   232                           15   5     5     351   354   8    8    5   435   432                           17   5     5     1009  991   10   8    5   308   326                           19   5     5     471   438   16   8    5   212   262                           21   5     5     348   336   -19  9    5   594   609                           -24  6     5     252   236   -17  9    5   897   946                           -16  6     5     484   505   -15  9    5   844   854                           -12  6     5     897   898   -13  9    5   348   293                           -10  6     5     541   566   -11  9    5   803   775                           -8   6     5     196   217   -9   9    5   1026  986                           -4   6     5     1538  1591  -7   9    5   1554  1503                          -2   6     5     908   927   -5   9    5   561   549                           0    6     5     734   745   -3   9    5   224   170                           2    6     5     587   589   1    9    5   778   781                           4    6     5     341   372   3    9    5   1102  1076                          6    6     5     936   947   5    9    5   709   696                           8    6     5     635   626   7    9    5   659   643                           10   6     5     981   969   9    9    5   306   297                           12   6     5     667   654   11   9    5   607   606                           16   6     5     168   169   13   9    5   535   513                           18   6     5     437   439   15   9    5   488   476                           20   6     5     640   621   17   9    5   407   401                           22   6     5     298   296   -18  10   5   491   509                           -23  7     5     256   268   -16  10   5   630   654                           -21  7     5     491   524   -12  10   5   569   559                           -19  7     5     689   713   -10  10   5   740   715                           -17  7     5     489   499   -8   10   5   1078  1057                          -15  7     5     260   243   -6   10   5   915   901                           -13  7     5     284   288   -4   10   5   216   233                           -11  7     5     648   656   -2   10   5   898   901                           -9   7     5     924   873   0    10   5   1174  1179                          -7   7     5     1244  1174  2    10   5   1215  1219                          -5   7     5     829   849   4    10   5   469   467                           -3   7     5     297   324   6    10   5   347   334                           -1   7     5     826   820   8    10   5   717   720                           1    7     5     1240  1242  10   10   5   934   944                           3    7     5     1159  1173  12   10   5   756   744                           5    7     5     614   609   14   10   5   193   209                           9    7     5     657   640   -11  11   5   243   212                           11   7     5     740   704   -3   11   5   196   189                           13   7     5     767   752   -1   11   5   330   333                           15   7     5     453   446   1    11   5   228   243                           17   7     5     195   164   3    11   5   142   194                           19   7     5     201   214   7    11   5   303   304                           -20  8     5     383   389   9    11   5   370   356                           -18  8     5     755   808   11   11   5   176   186                           -16  8     5     613   643   -12  12   5   373   364                           -14  8     5     705   731   -8   12   5   163   148                           -12  8     5     196   161   -6   12   5   200   186                           -10  8     5     1089  1061  -4   12   5   401   399                           -8   8     5     1104  1058  -2   12   5   224   201                           0    12    5     187   171   -16  2    6   153   145                           2    12    5     317   330   -12  2    6   900   871                           10   12    5     419   404   -10  2    6   1028  1025                          -7   13    5     1063  1074  -8   2    6   871   859                           -5   13    5     518   518   -6   2    6   553   534                           -1   13    5     436   458   -4   2    6   557   551                           1    13    5     803   801   -2   2    6   1821  1856                          3    13    5     770   783   0    2    6   1414  1459                          -26  0     6     168   159   2    2    6   696   714                           -22  0     6     259   264   4    2    6   205   201                           -20  0     6     1055  1068  6    2    6   559   583                           -18  0     6     651   649   8    2    6   729   767                           -14  0     6     481   480   10   2    6   1059  1096                          -12  0     6     1858  1781  12   2    6   672   669                           -10  0     6     4346  4129  14   2    6   409   399                           -8   0     6     1990  1879  16   2    6   285   265                           -6   0     6     226   153   18   2    6   366   359                           -4   0     6     1950  1962  20   2    6   532   525                           -2   0     6     6397  6139  22   2    6   394   382                           0    0     6     4640  4799  -23  3    6   149   150                           2    0     6     2292  2342  -21  3    6   523   533                           4    0     6     392   406   -19  3    6   1146  1181                          6    0     6     3260  3334  -17  3    6   939   974                           8    0     6     4099  4236  -15  3    6   1144  1207                          10   0     6     2108  2128  -13  3    6   760   762                           12   0     6     1057  1071  -11  3    6   1444  1455                          16   0     6     1002  1001  -9   3    6   2482  2526                          18   0     6     1154  1142  -7   3    6   1843  1928                          20   0     6     714   704   -5   3    6   2160  2210                          22   0     6     890   877   -3   3    6   339   352                           24   0     6     174   154   -1   3    6   1821  1868                          -21  1     6     214   225   1    3    6   1703  1736                          -19  1     6     545   531   3    3    6   1697  1729                          -17  1     6     622   654   5    3    6   607   619                           -15  1     6     711   696   7    3    6   794   801                           -13  1     6     660   634   9    3    6   678   663                           -11  1     6     932   903   11   3    6   301   279                           -9   1     6     1305  1314  13   3    6   539   538                           -7   1     6     1188  1178  17   3    6   248   244                           -5   1     6     1548  1549  21   3    6   358   350                           -3   1     6     250   235   23   3    6   321   331                           -1   1     6     1990  2006  -22  4    6   285   201                           3    1     6     879   904   -12  4    6   715   716                           5    1     6     525   552   -10  4    6   1609  1648                          7    1     6     178   203   -8   4    6   231   272                           9    1     6     223   243   -4   4    6   958   994                           11   1     6     175   154   -2   4    6   3027  3066                          13   1     6     485   471   0    4    6   2054  2118                          15   1     6     220   227   4    4    6   591   594                           17   1     6     212   180   6    4    6   1629  1663                          21   1     6     297   294   8    4    6   1830  1873                          23   1     6     212   179   10   4    6   747   747                           -24  2     6     164   124   16   4    6   669   652                           -22  2     6     177   175   18   4    6   398   390                           -20  2     6     287   293   22   4    6   316   305                           -18  2     6     423   412   -23  5    6   245   261                           -21  5     6     488   487   11   7    6   709   713                           -19  5     6     604   644   13   7    6   224   205                           -17  5     6     695   728   15   7    6   193   177                           -15  5     6     198   184   19   7    6   400   383                           -13  5     6     951   999   -20  8    6   396   426                           -11  5     6     1261  1283  -18  8    6   553   588                           -9   5     6     1355  1423  -16  8    6   683   685                           -7   5     6     1132  1157  -14  8    6   307   292                           -5   5     6     329   336   -12  8    6   353   364                           -3   5     6     1642  1671  -10  8    6   563   545                           -1   5     6     1763  1802  -8   8    6   1161  1114                          1    5     6     1946  1959  -6   8    6   828   798                           3    5     6     619   604   -4   8    6   278   272                           5    5     6     585   567   0    8    6   686   683                           7    5     6     1158  1171  2    8    6   1366  1346                          9    5     6     1337  1338  4    8    6   682   679                           11   5     6     1171  1158  6    8    6   464   440                           13   5     6     302   301   10   8    6   716   727                           15   5     6     269   271   12   8    6   791   791                           17   5     6     478   489   14   8    6   317   319                           19   5     6     639   631   16   8    6   171   156                           21   5     6     406   399   18   8    6   330   322                           -24  6     6     192   140   -19  9    6   522   549                           -20  6     6     446   475   -17  9    6   695   707                           -18  6     6     326   336   -15  9    6   458   444                           -14  6     6     176   128   -13  9    6   319   267                           -12  6     6     967   971   -11  9    6   907   883                           -10  6     6     1438  1419  -9   9    6   1309  1263                          -8   6     6     1313  1355  -7   9    6   1238  1206                          -6   6     6     609   622   -3   9    6   919   899                           -4   6     6     808   805   -1   9    6   1391  1386                          -2   6     6     2133  2161  1    9    6   1101  1119                          0    6     6     2171  2178  3    9    6   508   498                           2    6     6     1475  1503  5    9    6   373   376                           4    6     6     481   478   7    9    6   860   848                           6    6     6     1052  1051  9    9    6   764   760                           8    6     6     1630  1612  11   9    6   478   478                           10   6     6     1414  1395  13   9    6   168   157                           12   6     6     1020  1005  15   9    6   266   247                           14   6     6     538   526   -18  10   6   416   411                           16   6     6     387   397   -16  10   6   220   251                           18   6     6     561   548   -8   10   6   294   278                           20   6     6     792   769   -6   10   6   151   146                           -23  7     6     366   364   -4   10   6   184   177                           -19  7     6     425   460   -2   10   6   473   472                           -17  7     6     336   319   0    10   6   266   276                           -15  7     6     932   963   6    10   6   356   337                           -13  7     6     776   791   8    10   6   510   512                           -11  7     6     371   370   -15  11   6   364   382                           -9   7     6     557   536   -13  11   6   711   699                           -7   7     6     683   649   -11  11   6   425   382                           -5   7     6     1366  1318  -9   11   6   447   445                           -3   7     6     300   286   -5   11   6   443   442                           -1   7     6     206   207   -3   11   6   627   629                           5    7     6     416   404   -1   11   6   648   661                           9    7     6     501   474   1    11   6   933   936                           3    11    6     544   552   14   2    7   459   483                           5    11    6     235   221   16   2    7   539   519                           7    11    6     376   385   18   2    7   480   471                           9    11    6     897   897   20   2    7   689   679                           11   11    6     960   957   22   2    7   410   393                           -10  12    6     381   394   -23  3    7   214   221                           -8   12    6     674   683   -17  3    7   197   198                           -6   12    6     458   454   -15  3    7   160   44                            -2   12    6     257   287   -13  3    7   281   279                           0    12    6     475   473   -11  3    7   663   662                           2    12    6     567   578   -9   3    7   518   514                           4    12    6     243   256   -7   3    7   576   593                           -3   13    6     206   213   -5   3    7   136   128                           -1   13    6     214   150   -3   3    7   1036  1045                          1    13    6     212   216   -1   3    7   134   99                            -25  1     7     164   152   1    3    7   418   434                           -23  1     7     229   214   3    3    7   198   206                           -21  1     7     773   778   5    3    7   300   292                           -19  1     7     721   755   7    3    7   184   224                           -15  1     7     287   299   9    3    7   257   259                           -13  1     7     1836  1753  11   3    7   284   278                           -11  1     7     2904  2833  15   3    7   160   42                            -9   1     7     1092  1089  17   3    7   154   123                           -7   1     7     302   253   19   3    7   314   315                           -5   1     7     1076  1114  -22  4    7   406   409                           -3   1     7     3429  3499  -20  4    7   781   796                           -1   1     7     2714  2789  -18  4    7   557   560                           1    1     7     1565  1642  -16  4    7   426   449                           3    1     7     679   703   -14  4    7   552   593                           5    1     7     724   730   -12  4    7   1307  1323                          7    1     7     2078  2115  -10  4    7   1281  1289                          9    1     7     1697  1723  -8   4    7   717   708                           11   1     7     1464  1464  -4   4    7   878   894                           13   1     7     1006  1024  -2   4    7   1426  1464                          15   1     7     337   335   0    4    7   1322  1348                          17   1     7     852   857   2    4    7   422   419                           19   1     7     870   877   6    4    7   965   1010                          21   1     7     905   893   8    4    7   1150  1183                          23   1     7     321   316   10   4    7   756   743                           -24  2     7     407   391   12   4    7   615   624                           -20  2     7     614   611   14   4    7   248   281                           -18  2     7     494   511   16   4    7   670   671                           -16  2     7     729   751   18   4    7   726   722                           -14  2     7     1208  1282  20   4    7   534   541                           -12  2     7     690   685   -21  5    7   525   542                           -10  2     7     771   768   -19  5    7   272   299                           -8   2     7     407   415   -17  5    7   209   224                           -6   2     7     1821  1824  -13  5    7   1159  1168                          -4   2     7     307   326   -11  5    7   1845  1879                          -2   2     7     341   336   -9   5    7   807   841                           0    2     7     362   354   -5   5    7   1081  1098                          2    2     7     461   444   -3   5    7   2337  2385                          4    2     7     1229  1223  -1   5    7   2153  2189                          6    2     7     214   207   1    5    7   651   672                           10   2     7     155   94    3    5    7   664   664                           12   2     7     870   868   5    5    7   459   450                           7    5     7     1494  1491  16   8    7   211   187                           9    5     7     1159  1141  -19  9    7   330   347                           11   5     7     1176  1178  -15  9    7   220   260                           13   5     7     1095  1087  -9   9    7   492   466                           15   5     7     149   135   -7   9    7   263   257                           17   5     7     569   562   -5   9    7   244   261                           19   5     7     757   749   1    9    7   462   455                           21   5     7     825   807   3    9    7   359   336                           -22  6     7     443   451   5    9    7   385   381                           -16  6     7     692   730   7    9    7   144   99                            -14  6     7     1044  1074  9    9    7   413   413                           -12  6     7     555   530   13   9    7   475   461                           -10  6     7     547   544   15   9    7   340   323                           -8   6     7     619   587   -16  10   7   227   242                           -6   6     7     1104  1122  -14  10   7   733   691                           -4   6     7     1354  1396  -12  10   7   801   783                           -2   6     7     1077  1073  -10  10   7   828   804                           0    6     7     1294  1316  -8   10   7   500   492                           2    6     7     403   383   -6   10   7   340   347                           4    6     7     894   893   -4   10   7   961   957                           6    6     7     820   811   -2   10   7   984   998                           8    6     7     961   955   0    10   7   1288  1281                          10   6     7     926   933   2    10   7   675   684                           14   6     7     236   236   4    10   7   353   353                           16   6     7     157   143   6    10   7   716   721                           18   6     7     352   353   8    10   7   964   973                           20   6     7     186   243   10   10   7   1066  1063                          -21  7     7     239   280   12   10   7   393   402                           -19  7     7     259   256   -9   11   7   314   319                           -17  7     7     308   311   -7   11   7   211   243                           -15  7     7     295   277   -3   11   7   252   249                           -13  7     7     572   560   -1   11   7   258   271                           -11  7     7     570   587   1    11   7   445   464                           -9   7     7     798   752   3    11   7   450   464                           -7   7     7     432   406   9    11   7   362   368                           - 3  7     7     353   354   -10  12   7   354   343                           -1   7     7     1039  1002  -8   12   7   255   221                           1    7     7     1311  1294  -6   12   7   269   240                           3    7     7     739   724   -4   12   7   534   537                           7    7     7     687   673   -2   12   7   575   586                           9    7     7     1054  1041  0    12   7   946   936                           11   7     7     1271  1271  2    12   7   490   529                           13   7     7     454   468   6    12   7   286   290                           17   7     7     586   587   -26  0    8   638   638                           19   7     7     816   799   -24  0    8   668   642                           -20  8     7     341   342   -22  0    8   1188  1184                          -18  8     7     436   435   -20  0    8   582   578                           -16  8     7     616   619   -18  0    8   788   809                           -14  8     7     400   383   -16  0    8   1137  1175                          -12  8     7     251   231   -14  0    8   2316  2373                          -10  8     7     584   548   -12  0    8   2541  2449                          -8   8     7     629   616   -10  0    8   157   88                            -6   8     7     345   319   -8   0    8   522   502                           -2   8     7     452   444   -6   0    8   1469  1416                          0    8     7     185   164   -4   0    8   2818  2791                          10   8     7     160   171   -2   0    8   1987  2059                          0    0     8     861   849   -17  3    8   182   177                           2    0     8     663   691   -15  3    8   182   160                           4    0     8     240   245   -13  3    8   481   502                           6    0     8     1909  1960  -11  3    8   237   243                           8    0     8     1465  1506  -9   3    8   904   925                           10   0     8     1634  1603  -3   3    8   322   327                           12   0     8     1202  1199  -1   3    8   578   590                           14   0     8     311   301   1    3    8   301   295                           16   0     8     1016  1041  3    3    8   717   760                           18   0     8     657   650   5    3    8   463   458                           20   0     8     776   771   7    3    8   811   830                           22   0     8     240   243   9    3    8   597   594                           -21  1     8     242   219   11   3    8   840   845                           -19  1     8     316   321   13   3    8   191   168                           -17  1     8     252   257   15   3    8   1095  1106                          -15  1     8     414   438   17   3    8   1003  1004                          -13  1     8     297   297   19   3    8   682   667                           -11  1     8     542   561   21   3    8   279   308                           -9   1     8     591   583   -24  4    8   219   215                           -5   1     8     181   239   -22  4    8   625   629                           -3   1     8     229   227   -20  4    8   296   273                           -1   1     8     504   516   -18  4    8   529   540                           3    1     8     307   310   -16  4    8   352   379                           5    1     8     243   232   -14  4    8   942   951                           7    1     8     586   579   -12  4    8   1293  1297                          11   1     8     410   405   -8   4    8   199   209                           13   1     8     158   161   -6   4    8   307   314                           15   1     8     823   836   -4   4    8   1113  1130                          17   1     8     506   526   -2   4    8   810   818                           19   1     8     508   503   0    4    8   232   256                           21   1     8     202   181   2    4    8   842   872                           -26  2     8     223   203   4    4    8   377   398                           -24  2     8     371   349   6    4    8   676   659                           -22  2     8     354   359   8    4    8   367   335                           -18  2     8     238   248   10   4    8   513   507                           -16  2     8     412   421   12   4    8   993   1002                          -14  2     8     529   544   16   4    8   179   179                           -12  2     8     509   491   20   4    8   361   355                           -10  2     8     442   437   -23  5    8   570   559                           -8   2     8     159   133   -21  5    8   301   331                           -6   2     8     263   224   -17  5    8   393   407                           -4   2     8     344   352   -15  5    8   1073  1085                          -2   2     8     1015  1010  -13  5    8   794   792                           0    2     8     476   509   -11  5    8   1018  1021                          2    2     8     893   909   -9   5    8   432   423                           4    2     8     209   213   -7   5    8   921   953                           6    2     8     601   625   -5   5    8   1199  1224                          8    2     8     762   774   -3   5    8   1343  1359                          10   2     8     801   798   -1   5    8   1167  1207                          12   2     8     539   558   1    5    8   295   316                           16   2     8     410   404   3    5    8   563   559                           18   2     8     600   599   5    5    8   1218  1211                          20   2     8     427   430   7    5    8   835   816                           -23  3     8     164   190   9    5    8   920   909                           -21  3     8     396   411   11   5    8   164   158                           -19  3     8     163   191   13   5    8   403   415                           15   5     8     288   285   -11  9    8   187   201                           17   5     8     542   543   -7   9    8   452   449                           19   5     8     336   339   -5   9    8   499   490                           -22  6     8     449   466   -3   9    8   462   467                           -20  6     8     184   186   -1   9    8   299   299                           -18  6     8     255   253   1    9    8   145   141                           -16  6     8     637   619   3    9    8   352   329                           -14  6     8     927   926   5    9    8   476   487                           -12  6     8     868   871   7    9    8   418   406                           -10  6     8     451   420   9    9    8   539   550                           -4   6     8     859   834   13   9    8   165   160                           -2   6     8     1324  1285  -6   10   8   520   508                           0    6     8     833   802   -2   10   8   155   155                           2    6     8     1351  1328  0    10   8   184   212                           4    6     8     229   199   2    10   8   899   904                           6    6     8     772   753   4    10   8   807   795                           8    6     8     1250  1221  6    10   8   255   262                           10   6     8     1509  1503  10   10   8   662   664                           12   6     8     963   957   12   10   8   713   717                           16   6     8     652   651   -13  11   8   581   554                           18   6     8     865   867   -11  11   8   553   557                           -19  7     8     188   207   -9   11   8   568   566                           -15  7     8     476   473   -7   11   8   248   256                           -13  7     8     444   472   -5   11   8   722   709                           -11  7     8     550   554   -3   11   8   698   677                           -9   7     8     977   957   -1   11   8   1117  1123                          -7   7     8     174   177   1    11   8   673   678                           -5   7     8     676   658   5    11   8   261   255                           -3   7     8     687   680   7    11   8   753   758                           -1   7     8     1389  1370  9    11   8   888   906                           1    7     8     707   711   -8   12   8   202   201                           3    7     8     507   512   0    12   8   461   474                           7    7     8     379   372   -25  1    9   710   688                           9    7     8     532   549   -23  1    9   841   844                           13   7     8     165   137   -21  1    9   199   241                           15   7     8     346   348   -19  1    9   710   713                           17   7     8     172   132   -17  1    9   878   892                           -20  8     8     188   117   -15  1    9   1225  1219                          -16  8     8     203   229   -13  1    9   1122  1118                          -10  8     8     527   496   -11  1    9   235   232                           -8   8     8     219   207   -9   1    9   323   339                           -6   8     8     474   467   -7   1    9   242   219                           -4   8     8     272   247   -5   1    9   1208  1231                          -2   8     8     390   370   -3   1    9   1266  1278                          0    8     8     789   798   -1   1    9   613   648                           2    8     8     195   201   1    1    9   933   954                           4    8     8     485   485   3    1    9   207   207                           6    8     8     491   503   5    1    9   1154  1178                          8    8     8     822   816   7    1    9   874   860                           10   8     8     573   571   9    1    9   669   668                           12   8     8     324   319   11   1    9   725   740                           14   8     8     355   353   13   1    9   290   312                           16   8     8     576   583   15   1    9   483   498                           -17  9     8     313   304   19   1    9   288   327                           -15  9     8     480   477   21   1    9   177   148                           -13  9     8     479   479   -24  2    9   170   118                           -20  2     9     775   767   -17  5    9   691   702                           -18  2     9     705   701   -15  5    9   678   699                           -12  2     9     978   978   -13  5    9   801   828                           -10  2     9     1311  1299  -11  5    9   223   176                           -8   2     9     226   185   -7   5    9   467   467                           -6   2     9     284   305   -5   5    9   454   447                           -4   2     9     166   133   -3   5    9   853   826                           -2   2     9     213   223   -1   5    9   551   537                           0    2     9     349   321   1    5    9   1425  1391                          2    2     9     442   441   3    5    9   456   441                           4    2     9     1032  1056  5    5    9   564   555                           6    2     9     1509  1472  7    5    9   575   579                           8    2     9     434   434   9    5    9   667   670                           10   2     9     532   538   11   5    9   792   778                           12   2     9     316   302   15   5    9   227   259                           14   2     9     1475  1495  -22  6    9   184   198                           16   2     9     830   832   -20  6    9   354   350                           18   2     9     567   588   -16  6    9   746   764                           20   2     9     298   281   -14  6    9   751   772                           -19  3     9     180   167   -12  6    9   698   705                           -17  3     9     204   207   -10  6    9   607   588                           -9   3     9     221   174   -8   6    9   524   504                           -7   3     9     251   240   -6   6    9   835   798                           -5   3     9     155   158   -4   6    9   631   604                           -1   3     9     185   185   -2   6    9   934   912                           1    3     9     208   204   0    6    9   355   359                           3    3     9     898   930   2    6    9   710   684                           7    3     9     556   538   8    6    9   436   432                           9    3     9     312   316   10   6    9   220   229                           11   3     9     541   534   14   6    9   334   338                           15   3     9     378   384   -19  7    9   297   285                           17   3     9     465   485   -17  7    9   492   507                           -24  4     9     452   444   -15  7    9   273   292                           -22  4     9     199   183   -13  7    9   184   189                           -20  4     9     441   436   -11  7    9   193   182                           -18  4     9     883   889   -7   7    9   271   286                           -16  4     9     822   843   -5   7    9   523   513                           -14  4     9     458   460   -3   7    9   367   364                           -12  4     9     228   200   -1   7    9   629   608                           -10  4     9     921   913   1    7    9   222   226                           -8   4     9     938   928   3    7    9   259   276                           -6   4     9     1003  1037  5    7    9   429   451                           -4   4     9     1124  1155  7    7    9   904   906                           -2   4     9     238   258   9    7    9   801   798                           0    4     9     150   140   13   7    9   255   210                           2    4     9     828   830   15   7    9   617   620                           4    4     9     1261  1246  -18  8    9   488   500                           6    4     9     993   979   -12  8    9   436   423                           8    4     9     625   618   -10  8    9   918   899                           12   4     9     595   601   -8   8    9   370   363                           14   4     9     821   825   -2   8    9   503   487                           16   4     9     790   802   0    8    9   243   235                           18   4     9     331   318   2    8    9   271   276                           -23  5     9     598   597   4    8    9   471   482                           -21  5     9     188   178   6    8    9   293   285                           -19  5     9     530   563   10   8    9   154   127                           12   8     9     293   280   -9   1    10  634   622                           14   8     9     439   433   -7   1    10  342   347                           -17  9     9     311   292   -5   1    10  931   937                           -15  9     9     426   432   -1   1    10  609   632                           -9   9     9     497   490   1    1    10  282   292                           -7   9     9     1112  1083  3    1    10  1326  1360                          -5   9     9     498   491   5    1    10  1158  1159                          -3   9     9     273   276   11   1    10  551   567                           1    9     9     1143  1136  13   1    10  983   1004                          3    9     9     1128  1142  15   1    10  356   356                           5    9     9     578   571   17   1    10  242   263                           7    9     9     427   414   -20  2    10  228   254                           9    9     9     223   215   -18  2    10  386   381                           11   9     9     701   698   -16  2    10  385   369                           13   9     9     582   594   -14  2    10  485   445                           -14  10    9     598   599   -8   2    10  297   259                           -12  10    9     395   369   -6   2    10  574   588                           -10  10    9     169   168   -4   2    10  370   403                           -8   10    9     648   631   -2   2    10  249   235                           -6   10    9     918   884   2    2    10  418   415                           -4   10    9     559   558   4    2    10  381   359                           -2   10    9     658   665   6    2    10  586   585                           2    10    9     455   470   12   2    10  284   314                           4    10    9     414   402   14   2    10  336   350                           6    10    9     504   504   -21  3    10  780   777                           8    10    9     513   516   -19  3    10  1052  1040                          -7   11    9     265   274   -17  3    10  488   499                           -5   11    9     263   286   -15  3    10  308   328                           -1   11    9     374   367   -11  3    10  1063  1103                          1    11    9     403   402   -9   3    10  966   956                           3    11    9     383   368   -7   3    10  1271  1274                          -24  0     10    689   670   -5   3    10  1447  1378                          -20  0     10    771   779   -3   3    10  212   242                           -18  0     10    870   848   -1   3    10  652   683                           -16  0     10    831   818   1    3    10  1254  1224                          -14  0     10    909   900   3    3    10  2069  2038                          -12  0     10    202   212   5    3    10  1702  1689                          -10  0     10    599   575   9    3    10  185   222                           -8   0     10    416   419   11   3    10  799   809                           -6   0     10    1285  1259  13   3    10  1207  1219                          -4   0     10    1070  1101  15   3    10  641   662                           -2   0     10    221   234   17   3    10  232   238                           0    0     10    389   383   -22  4    10  187   178                           2    0     10    475   483   -20  4    10  223   218                           4    0     10    1544  1490  -18  4    10  201   186                           6    0     10    520   529   -16  4    10  236   225                           8    0     10    678   686   -14  4    10  448   467                           10   0     10    225   214   -8   4    10  454   466                           12   0     10    551   560   -4   4    10  454   459                           16   0     10    509   500   -2   4    10  348   328                           18   0     10    199   217   0    4    10  394   387                           -21  1     10    464   458   2    4    10  428   422                           -19  1     10    557   554   4    4    10  229   232                           -17  1     10    199   226   6    4    10  677   659                           -13  1     10    339   341   8    4    10  479   488                           -11  1     10    713   705   14   4    10  401   401                           16   4     10    720   722   0    8    10  797   792                           18   4     10    242   241   2    8    10  926   937                           -19  5     10    521   538   4    8    10  813   820                           -17  5     10    859   877   6    8    10  720   729                           -15  5     10    830   840   8    8    10  330   346                           -13  5     10    301   338   10   8    10  428   432                           -11  5     10    392   357   12   8    10  583   576                           -9   5     10    786   784   -15  9    10  437   458                           - 7  5     10    1346  1299  -11  9    10  398   401                           -5   5     10    661   632   -9   9    10  824   801                           -3   5     10    329   291   -7   9    10  879   848                           -1   5     10    315   295   -5   9    10  554   528                           1    5     10    1219  1181  -1   9    10  492   487                           3    5     10    586   555   1    9    10  753   749                           5    5     10    386   395   3    9    10  674   681                           7    5     10    243   230   5    9    10  357   360                           9    5     10    496   484   9    9    10  333   346                           11   5     10    402   391   11   9    10  371   349                           13   5     10    221   237   -10  10   10  425   391                           15   5     10    238   216   -8   10   10  799   770                           -20  6     10    406   442   -6   10   10  373   356                           -18  6     10    426   465   -2   10   10  232   232                           -16  6     10    372   355   0    10   10  516   523                           -14  6     10    539   561   2    10   10  544   567                           -8   6     10    277   233   4    10   10  253   266                           -6   6     10    796   763   6    10   10  261   224                           -4   6     10    572   546   8    10   10  170   58                            -2   6     10    327   345   -7   11   10  418   381                           2    6     10    519   509   -5   11   10  351   338                           4    6     10    565   578   -3   11   10  483   481                           6    6     10    494   524   -1   11   10  273   238                           12   6     10    331   324   1    11   10  161   164                           14   6     10    336   365   3    11   10  210   128                           19   7     10    405   391   -23  1    11  257   269                           17   7     10    170   126   -21  1    11  216   223                           15   7     10    191   211   -19  1    11  394   382                           13   7     10    407   408   -17  1    11  569   570                           11   7     10    855   860   -15  1    11  827   813                           -5   7     10    293   277   -13  1    11  339   328                           -3   7     10    352   345   -11  1    11  535   521                           -1   7     10    519   499   -9   1    11  722   696                           1    7     10    425   422   -7   1    11  1110  1121                          3    7     10    694   679   -5   1    11  832   834                           5    7     10    452   452   -3   1    11  697   693                           7    7     10    301   287   -1   1    11  1031  981                           9    7     10    290   249   1    1    11  1063  1029                          11   7     10    257   249   3    1    11  924   921                           13   7     10    423   418   5    1    11  538   521                           18   8     10    502   497   7    1    11  938   940                           16   8     10    542   560   9    1    11  660   678                           14   8     10    179   144   11   1    11  553   565                           10   8     10    542   529   15   1    11  328   343                           -8   8     10    1016  985   17   1    11  287   302                           -6   8     10    766   748   -22  2    11  281   267                           -4   8     10    474   453   -20  2    11  606   590                           -2   8     10    256   249   -18  2    11  419   401                           -16  2     11    649   636   -5   5    11  555   514                           -14  2     11    688   686   -3   5    11  550   529                           -12  2     11    406   387   -1   5    11  626   614                           -10  2     11    1037  1023  1    5    11  438   420                           -8   2     11    1539  1534  3    5    11  436   426                           -6   2     11    2132  2120  5    5    11  443   443                           -4   2     11    805   777   7    5    11  889   897                           -2   2     11    837   776   9    5    11  309   338                           0    2     11    1058  1011  11   5    11  301   303                           2    2     11    2332  2302  15   5    11  500   506                           4    2     11    1530  1514  -18  6    11  302   290                           6    2     11    336   337   -16  6    11  179   166                           10   2     11    662   664   -10  6    11  191   197                           12   2     11    1014  1036  -6   6    11  479   477                           14   2     11    663   681   -4   6    11  277   261                           16   2     11    263   293   2    6    11  359   359                           18   2     11    229   247   4    6    11  463   464                           -23  3     11    187   198   8    6    11  230   203                           -17  3     11    214   186   10   6    11  183   159                           -13  3     11    231   221   12   6    11  167   146                           -9   3     11    673   672   -19  7    11  303   338                           -7   3     11    233   215   -17  7    11  490   488                           -3   3     11    363   367   -15  7    11  363   347                           -1   3     11    333   291   -11  7    11  259   304                           1    3     11    288   287   -9   7    11  684   681                           3    3     11    405   403   -7   7    11  817   799                           5    3     11    803   811   -5   7    11  642   625                           7    3     11    359   386   -3   7    11  310   236                           11   3     11    310   342   -1   7    11  625   629                           13   3     11    519   539   1    7    11  881   876                           15   3     11    442   445   3    7    11  922   921                           17   3     11    270   239   5    7    11  568   549                           -22  4     11    326   321   9    7    11  434   444                           -20  4     11    681   672   11   7    11  587   604                           -18  4     11    813   807   13   7    11  532   549                           -16  4     11    878   873   -16  8    11  489   506                           -14  4     11    279   261   -14  8    11  312   304                           -12  4     11    542   560   -12  8    11  308   286                           -10  4     11    1253  1255  -10  8    11  776   725                           -8   4     11    1611  1584  -8   8    11  1026  1003                          -6   4     11    1377  1352  -6   8    11  930   915                           -4   4     11    478   453   -4   8    11  186   134                           -2   4     11    943   934   -2   8    11  639   638                           0    4     11    1665  1638  0    8    11  851   826                           2    4     11    1490  1469  2    8    11  791   785                           4    4     11    1172  1148  4    8    11  531   544                           6    4     11    250   232   6    8    11  189   184                           8    4     11    548   560   8    8    11  305   302                           10   4     11    711   721   10   8    11  172   152                           12   4     11    750   756   -13  9    11  320   294                           14   4     11    357   321   -11  9    11  610   599                           -17  5     11    176   154   -9   9    11  926   923                           -15  5     11    695   718   -7   9    11  550   556                           -13  5     11    378   350   -1   9    11  429   435                           -9   5     11    355   359   1    9    11  759   774                           -7   5     11    671   658   3    9    11  498   515                           5    9     11    545   547   10   2    12  500   507                           7    9     11    398   383   12   2    12  422   426                           9    9     11    346   363   -21  3    12  534   509                           10   10    11    579   559   -19  3    12  721   700                           -8   10    11    680   666   -17  3    12  907   886                           -6   10    11    374   392   -15  3    12  776   765                           -2   10    11    341   344   -13  3    12  459   400                           0    10    11    629   645   -11  3    12  1201  1226                          2    10    11    556   561   -9   3    12  1412  1406                          20   0     12    383   388   -7   3    12  1818  1771                          18   0     12    443   397   -5   3    12  614   589                           16   0     12    603   557   -3   3    12  702   690                           12   0     12    1219  1196  -1   3    12  1095  1062                          10   0     12    826   814   1    3    12  1483  1464                          -8   0     12    841   846   3    3    12  1258  1267                          -4   0     12    1490  1496  5    3    12  313   298                           -2   0     12    1574  1561  9    3    12  448   462                           0    0     12    1136  1090  11   3    12  859   871                           2    0     12    405   405   13   3    12  611   634                           4    0     12    717   700   15   3    12  192   202                           6    0     12    1228  1243  -18  4    12  199   120                           8    0     12    1042  1060  -16  4    12  312   298                           10   0     12    597   623   -14  4    12  218   153                           12   0     12    445   443   -12  4    12  343   358                           14   0     12    321   320   -6   4    12  190   197                           16   0     12    434   471   -4   4    12  955   936                           21   1     12    354   312   -2   4    12  671   644                           19   1     12    259   242   2    4    12  268   258                           17   1     12    438   432   4    4    12  773   794                           15   1     12    593   571   6    4    12  845   871                           11   1     12    689   674   8    4    12  225   234                           -9   1     12    875   874   14   4    12  425   419                           -7   1     12    1142  1148  -19  5    12  500   485                           -5   1     12    424   386   -17  5    12  378   358                           -3   1     12    323   311   -13  5    12  327   347                           -1   1     12    634   610   -11  5    12  748   730                           1    1     12    1012  1009  -9   5    12  788   786                           3    1     12    678   655   -7   5    12  308   292                           5    1     12    402   382   -5   5    12  260   223                           7    1     12    179   128   -3   5    12  705   690                           11   1     12    564   571   -1   5    12  813   805                           13   1     12    456   483   1    5    12  636   646                           15   1     12    205   136   3    5    12  183   171                           -20  2     12    199   172   5    5    12  267   292                           -18  2     12    211   208   7    5    12  475   472                           -16  2     12    329   297   9    5    12  614   612                           -12  2     12    289   289   11   5    12  324   352                           -10  2     12    587   582   -18  6    12  281   302                           -8   2     12    511   524   -16  6    12  400   434                           -6   2     12    429   421   -12  6    12  454   446                           -4   2     12    360   330   -10  6    12  631   634                           -2   2     12    515   501   -8   6    12  630   644                           0    2     12    667   653   -6   6    12  479   467                           2    2     12    588   571   -4   6    12  522   510                           6    2     12    261   255   -2   6    12  867   857                           8    2     12    314   326   0    6    12  786   787                           2    6     12    735   738   -8   2    13  1042  1036                          6    6     12    540   533   -6   2    13  858   834                           8    6     12    504   517   -2   2    13  207   210                           10   6     12    775   786   0    2    13  646   629                           12   6     12    519   541   2    2    13  1190  1188                          -17  7     12    354   341   4    2    13  769   771                           -15  7     12    481   486   6    2    13  177   155                           -11  7     12    417   391   10   2    13  896   892                           -9   7     12    504   489   12   2    13  706   729                           -7   7     12    723   721   -19  3    13  179   158                           -5   7     12    354   356   -11  3    13  206   168                           -3   7     12    257   247   -9   3    13  368   364                           1    7     12    248   276   -7   3    13  290   315                           3    7     12    541   526   -5   3    13  371   339                           7    7     12    272   284   -1   3    13  435   424                           9    7     12    247   234   1    3    13  464   462                           -12  8     12    367   356   3    3    13  220   190                           -10  8     12    779   757   5    3    13  259   265                           -8   8     12    839   850   7    3    13  208   208                           -6   8     12    406   404   9    3    13  229   250                           -4   8     12    202   212   -20  4    13  457   456                           -2   8     12    333   354   - 18 4    13  441   410                           0    8     12    932   935   -14  4    13  459   452                           2    8     12    808   823   -12  4    13  773   789                           4    8     12    700   692   -10  4    13  715   711                           6    8     12    281   274   -8   4    13  635   606                           8    8     12    453   489   -4   4    13  431   419                           -11  9     12    566   566   -2   4    13  615   591                           -9   9     12    795   762   0    4    13  623   613                           -7   9     12    596   570   2    4    13  631   642                           -3   9     12    447   467   8    4    13  514   527                           -1   9     12    631   646   10   4    13  608   633                           1    9     12    611   604   12   4    13  421   418                           3    9     12    248   245   -15  5    13  240   261                           0    10    12    274   227   -13  5    13  662   664                           -21  1     13    407   391   -11  5    13  278   268                           -15  1     13    356   358   -5   5    13  702   711                           -13  1     13    1050  1026  -3   5    13  747   732                           -11  1     13    603   601   -1   5    13  355   356                           -9   1     13    281   281   1    5    13  432   431                           -7   1     13    273   207   5    5    13  434   446                           -5   1     13    944   928   7    5    13  479   466                           -3   1     13    1088  1066  9    5    13  631   645                           -1   1     13    668   638   11   5    13  678   674                           1    1     13    397   423   -16  6    13  473   483                           5    1     13    692   678   -14  6    13  223   241                           7    1     13    604   617   -8   6    13  313   316                           9    1     13    791   809   -6   6    13  440   442                           11   1     13    799   831   -4   6    13  346   345                           15   1     13    207   224   -2   6    13  567   574                           -20  2     13    464   451   0    6    13  320   305                           -18  2     13    556   518   2    6    13  311   327                           -16  2     13    727   699   4    6    13  364   369                           -14  2     13    213   211   6    6    13  520   547                           -12  2     13    597   581   8    6    13  435   459                           -10  2     13    624   627   -13  7    13  258   266                           -11  7     13    520   514   8    2    14  521   531                           -9   7     13    652   637   10   2    14  486   475                           -7   7     13    255   281   12   2    14  177   134                           -3   7     13    383   359   -15  3    14  235   249                           -1   7     13    675   685   -13  3    14  270   275                           1    7     13    817   827   -9   3    14  259   222                           3    7     13    530   525   -7   3    14  397   374                           7    7     13    447   451   -3   3    14  165   102                           9    7     13    823   822   1    3    14  767   771                           -12  8     13    298   279   3    3    14  284   326                           -10  8     13    258   245   7    3    14  212   223                           -8   8     13    395   418   9    3    14  562   584                           -6   8     13    280   273   11   3    14  425   439                           2    8     13    354   354   -18  4    14  264   278                           4    8     13    172   169   -16  4    14  409   389                           6    8     13    262   235   -14  4    14  546   547                           -7   9     13    188   152   -10  4    14  480   483                           -5   9     13    183   157   -8   4    14  186   222                           -3   9     13    219   173   -6   4    14  415   406                           -1   9     13    587   569   -4   4    14  354   330                           -20  0     14    282   272   2    4    14  190   195                           18   0     14    473   470   4    4    14  198   197                           16   0     14    764   749   8    4    14  174   209                           4    0     14    1155  1124  10   4    14  428   453                           2    0     14    357   325   -17  5    14  427   426                           0    0     14    264   316   -15  5    14  461   453                           -8   0     14    384   415   -13  5    14  384   398                           -6   0     14    884   871   -11  5    14  322   348                           -4   0     14    1054  1032  -7   5    14  413   423                           -2   0     14    265   282   -5   5    14  522   536                           0    0     14    541   525   -3   5    14  541   553                           2    0     14    266   269   -1   5    14  406   410                           4    0     14    604   618   3    5    14  310   336                           6    0     14    577   576   5    5    14  329   360                           8    0     14    843   882   7    5    14  496   529                           10   0     14    852   869   9    5    14  225   270                           12   0     14    229   225   -14  6    14  449   455                           -15  1     14    189   143   - 12 6    14  250   268                           -7   1     14    446   441   -6   6    14  311   302                           -3   1     14    188   213   -4   6    14  446   426                           1    1     14    566   550   -2   6    14  417   440                           3    1     14    327   327   0    6    14  682   673                           9    1     14    414   432   2    6    14  388   379                           11   1     14    196   193   6    6    14  499   532                           -16  2     14    336   320   8    6    14  745   778                           -14  2     14    325   299   -13  7    14  195   179                           -12  2     14    231   232   -11  7    14  415   417                           -4   2     14    343   341   -7   7    14  431   417                           -2   2     14    391   375   -5   7    14  428   411                           0    2     14    500   497   -3   7    14  627   600                           2    2     14    251   267   -1   7    14  394   391                           6    2     14    436   420   1    7    14  256   250                           3    7     14    360   332   -7   7    15  202   227                           5    7     14    376   364   -5   7    15  323   322                           -4   8     14    237   264   -3   7    15  553   538                           -2   8     14    566   565   -1   7    15  449   428                           0    8     14    416   411   -14  0    16  395   401                           -17  1     15    593   569   -8   0    16  578   602                           -15  1     15    773   752   -6   0    16  1010  1026                          -13  1     15    267   266   -4   0    16  468   474                           -7   1     15    547   557   2    0    16  768   793                           -5   1     15    761   764   4    0    16  461   461                           -3   1     15    449   469   -7   1    16  396   386                           -1   1     15    473   479   -5   1    16  241   230                           1    1     15    253   212   1    1    16  383   367                           3    1     15    489   496   3    1    16  591   594                           5    1     15    552   585   -14  2    16  260   263                           7    1     15    480   513   -8   2    16  355   362                           9    1     15    494   490   -6   2    16  400   411                           -12  2     15    329   305   -4   2    16  321   336                           -8   2     15    352   343   -2   2    16  194   164                           0    2     15    417   405   2    2    16  259   291                           4    2     15    496   501   4    2    16  320   348                           6    2     15    270   272   -11  3    16  166   109                           8    2     15    244   279   -9   3    16  227   244                           -11  3     15    205   161   -7   3    16  632   666                           1    3     15    251   219   -5   3    16  438   457                           5    3     15    186   179   -1   3    16  181   182                           7    3     15    171   149   1    3    16  696   702                           -16  4     15    334   347   3    3    16  849   874                           -14  4     15    307   320   5    3    16  274   251                           -10  4     15    176   106   -10  4    16  213   158                           -8   4     15    243   246   -6   4    16  459   449                           -6   4     15    431   454   -2   4    16  179   158                           -4   4     15    271   295   0    4    16  253   234                           2    4     15    358   376   2    4    16  194   215                           4    4     15    440   454   -9   5    16  561   590                           6    4     15    326   346   -7   5    16  422   432                           8    4     15    209   195   -5   5    16  295   318                           -13  5     15    226   196   -3   5    16  234   199                           -7   5     15    358   334   -1   5    16  299   307                           - 5  5     15    584   561   1    5    16  312   326                           -3   5     15    305   273   -9   1    17  518   537                           -1   5     15    516   520   -7   1    17  758   808                           1    5     15    342   346   -5   1    17  205   213                           3    5     15    300   295   1    1    17  576   600                           5    5     15    449   475   -10  2    17  339   336                           -12  6     15    438   422   -8   2    17  964   986                           -8   6     15    515   518   -6   2    17  595   624                           -6   6     15    375   386   -2   2    17  221   259                           -4   6     15    345   375   0    2    17  857   877                           -2   6     15    390   414   2    2    17  917   927                           0    6     15    235   210   -5   3    17  199   182                           2    6     15    178   153   -1   3    17  233   235                           ______________________________________                                    

Significantly, the parent Mo₂ S₄ (Et₂ NCS₂)₂ moiety appears as an essentially intact unit in the cluster, with the Mo-Mo bond length decreased very slightly (from 2.814 Å to 2.783 Å) and the Mo-S-Mo bridge angles and bond lengths little changed. However, the dihedral angle between the MoS₁ S₁ ' and Mo'S₁ S₁ ' planes has opened up from 147.9° to 164.4°, and the initially terminal Mo═S bonds have elongated from 2.09 Å to 2.316 Å as their role changes to a bridging μ₃ mode, bound to two Co atoms as well as the original Mo. The binding of two acetonitrile molecules also raises the overall cluster electron count to 60 e⁻, the predicted number for a stable M₄ cluster with six M-M bonds.

EXAMPLE 6 Production of (Bu₂ NCS₂)₂ Mo₂ (μ³ -S)₄ Cu₂ Cl₂

A sample of (i-Bu₂ NCS₂)₂ Mo₂ S₄ (100 mg, 0.137 mmol) was dissolved in 15 ml warm CH₃ CN, and solid CuCl (54 mg, 0.548 mmol) added. The mixture was stirred for 3 minutes, filtered, and the filtrate allowed to stand for 1 hour. The resulting fine red-brown crystalline solid was filtered and dried (yield: 113 mg). Anal. Calc. for C₁₈ H₃₆ N₂ S₈ Mo₂ Cu₂ Cl₂ : C, 23.33; H, 3.92; N, 3.02; S, 27.67; Mo, 20.70; Cu, 13.71; Cl, 7.65. Found C, 24.38; H, 3.83; N, 3.11; S, 26.82; Mo, 20.51; Cu, 12.94; Cl, 7.55.

A single crystal x-ray diffraction study was carried out on the product. The structure is illustrated in FIG. 2.

EXAMPLE 7 Hydrotreating Catalyst

An amount of the Example 5 material (0.80 gm) was decomposed on a model feed (5% dibenzothiophene/decalin) at 350° C. and 3150 KPa H₂ in a modified batch autoclave and gave an extremely high desulfurization rate. A crude zero order rate constant derived from operating data obtained between 2 and 4 hours was determined to be 160×10¹⁶ molecules DBT/g. cat. precursor/sec. This material was therefore found to be an effective HDS catalyst.

It is to be understood that the above disclosure is by way of specific example and that numerous modifications and variations of the invention are available to those of ordinary skill in the art without departing from the true spirit and scope of the invention. 

We claim as our invention:
 1. A composition of matter containing a heterometallic thiocubane cluster selected from compositions having the formula

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.2 L.sub.2.sup.3,

and

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.3

wherein: M¹ is Re, V, Mo or W, M² is Co, Cr, Cu, Ni or Fe, L¹ is a bidentate sulfur and/or nitrogen bearing ligand, and L² is a monodentate S, N, P or O donor ligand, L³ is CO, a monodentate anion ligand selected from halide, mercaptide or alkoxide anion ligands, or O, N, P or S containing monodentate donor ligand, andwherein (M₂ ¹ M₂ ² S₄) forms said heterometallic thiocubane cluster.
 2. The composition of claim 1 wherein M¹ is Mo or W.
 3. The composition of claim 1 wherein M¹ is Mo.
 4. The composition of claim 1 wherein M¹ is W.
 5. The composition of claim 1 wherein M² is Co.
 6. The composition of claim 3 wherein M² is Co.
 7. The composition of claim 4 wherein M² is Co.
 8. The composition of claim 1 wherein M² is Cu.
 9. The composition of claim 3 wherein M² is Cu.
 10. The composition of claim 4 wherein M² is Cu.
 11. The composition of claim 1 wherein said bidentate ligand, L¹, is selected from the group of xanthate, dithiophosphinate, dithiophosphate, o-aminobenzenethiolate, and dithiocarbamate.
 12. The composition of claim 1 wherein said bidentate ligand, L¹, is S₂ CNR₂ and wherein R is independently H or a hydrocarbyl group having from 1 to 12 carbon atoms.
 13. The composition of claim 12 wherein each R is C₂ H₅.
 14. The composition of claim 2 wherein said bidentate ligand, L¹, is S₂ CN(C₂ H₅)₂.
 15. The composition of claim 5 wherein said bidentate ligand, L¹, is S₂ CN(C₂ H₅)₂.
 16. The composition of claim 6 wherein said bidentate ligand, L¹, is S₂ CN(C₂ H₅)₂.
 17. The composition of claim 7 wherein said bidentate ligand, L¹, is S₂ CN(C₂ H₅)₂.
 18. The composition of claim 1 wherein said monodentate donor ligand, L², is acetonitrile.
 19. The composition of claim 2 wherein said monodentate donor ligand, L², is acetonitrile.
 20. The composition of claim 14 wherein said monodentate donor ligand, L², is acetonitrile.
 21. The composition of claim 18 wherein said monodentate donor ligand, L², is acetonitrile.
 22. The composition of claim 16 wherein said monodentate donor ligand, L², is acetonitrile.
 23. The composition of claim 17 wherein said monodentate donor ligand, L², is acetonitrile.
 24. The composition of claim 9 wherein said composition has the formula

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.3

and wherein L³ is Cl.
 25. The composition of claim 9 wherein said composition has the formula

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.3

and wherein L³ is CO.
 26. The composition of claim 10 wherein said composition has the formula

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.3

and wherein L³ is Cl.
 27. The composition of claim 10 wherein said composition has the formula

    (M.sub.2.sup.1 M.sub.2.sup.2 S.sub.4)L.sub.2.sup.1 L.sub.2.sup.3

and wherein L³ is CO. 